CN106280496B

CN106280496B - Polycarbonate resin composition

Info

Publication number: CN106280496B
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: 2019-09-10
Anticipated expiration: 2032-10-02
Also published as: TWI604012B; JP6106593B2; CN103857745B; JPWO2013051557A1; WO2013051557A1; TWI586754B; CN106280496A; CN103857745A; KR101971751B1; KR20140077164A; TW201634578A; TW201323517A

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 which contains (A) 99.9-96 parts by mass of a polycarbonate resin and (B) 0.1-4 parts by mass of titanium oxide, wherein the polycarbonate resin composition (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) having a repeating unit represented by the formula (I) in the main chain and a constituent unit represented by the formula (II) in an amount of 2 to 20% by mass, n is 25 to 65, and (A-2) having a repeating unit represented by the formula (I) in the main chain and a constituent unit represented by the formula (II) in an amount of 2 to 20% by massThe amount% of the constituent unit represented by the formula (II), wherein n is 70 to 350.

Description

Polycarbonate-based resin composition

The application is application number: 2012800487670, PCT Application No.: and 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 compositions.

Background technique

Mechanical strength, electrical characteristics, the transparency of polycarbonate resin etc. are excellent, are widely used as engineering plastics in electricity In the various fields such as gas-field of electronic device, automotive field.In mobile phone, Portable table type machine, digital camera, video recorder, electronic work Also polycarbonate resin is utilized in the shell of tool etc., these on the way in the presence of operation when fall a possibility that waiting, therefore resistance to punching Hitting property is important, and appearance design (especially color) is also important factor.

In addition, the coloring of resin material is to be relatively easy to, coloury resin material is effectively utilised at one's side ?.Especially largely use white, grey etc..On the other hand, it is known to polycarbonate-made of being copolymerized polysiloxane Poly organo alkyl copolymer (hereinafter sometimes referred to PC-PDMS.).The excellents such as the impact resistance of PC-PDMS, therefore by the phase It is ready to use in the purposes.It should be noted that described important with impact resistance on the way, on the other hand, appearance design is also important, It is therefore desirable for using titanium oxide as pigment.

Past, it is known that pass through the white appearance of the combination of PC-PDMS and titanium oxide and there is good impact resistant strength Composition.Such as the excellent and reflectivity Characteristics such as the mechanical properties such as known impact resistance, rigidity, optical characteristics are also excellent Polycarbonate-based resin composition (referring to patent document 1).According to patent document 1, the content of titanium oxide is 5~10% to contain There is the composition of PC-PDMS to show good reflectivity and mechanical strength.In addition, known in another example do not adding phosphorus Excellent anti-flammability is shown in the case where flame retardant, halogenated flame retardant and in high reflectivity, high light-proofness and thermostabilization Property excellent polycarbonate-based resin composition (referring to patent document 2).According to patent document 2, the content of titanium oxide is 5~ 50% composition containing PC-PDMS shows good reflectivity and Izod impact strength and anti-flammability.

The composition recorded in these documents shows high reflective character, but on the other hand containing due to titanium oxide Amount is more, therefore its intensity is lower than intensity possessed by original PC-PDMS, and uses on the way described, and specific gravity is greater than appropriate value, It is therefore contemplated that developing with good reflectivity and mechanical strength etc. and the less combination containing PC-PDMS of titanium oxide content Object.

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

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 5-320519 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2004-91567 bulletin

Patent document 3: Japanese Unexamined Patent Application Publication 2007-509208 bulletin

Summary of the invention

Invent solved project

In the composition containing PC-PDMS recorded in patent document 3, as the means for improving anti-flammability, use few Titanium oxide is measured, but there is no record for color appearance.

Therefore, the issue of the present invention is to provide a kind of polycarbonate-based resin compositions, are maintaining polycarbonate-poly- The excellent characteristic of organosiloxane copolymer simultaneously, has excellent color appearance.

The means to solve the problem

The inventors of the present invention have carried out research extensively and profoundly, as a result, it has been found that, if polycarbonate-poly organo alkyl copolymer In polysiloxane chain length, then be difficult to show intensity, therefore in order to show impact resistance, need more than a certain amount of poly- silicon The length of oxygen alkane chain length, and, if polysiloxanes chain length is long, although can express good intensity, the meeting of formed products surface The striped appearance for generating black is bad, and it was found that, if under given conditions, can have maintaining polycarbonate-to gather With excellent color appearance while the characteristic of organic siloxane copolymer.

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

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

(A) polycarbonate-based resin includes:

Polycarbonate -5~100 mass % of poly organo alkyl copolymer (A-1), polycarbonate-polysiloxane are total 0~95 mass % of aromatic copolycarbonate (A-3) other than 0~95 mass % of polymers (A-2) and (A-1) and (A-2),

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

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

[changing 1]

[in formula, R¹And R²Separately indicate halogen atom, the alkyl of carbon atom number 1~6 or the alkane of carbon atom number 1~6 Oxygroup, X indicate that singly-bound, the alkylidene of carbon atom number 1~8, the alkylidene radical of carbon atom number 2~8, the ring of carbon atom number 5~15 are sub- Ring alkylidene radical ,-the S- ,-SO- ,-SO of alkyl, carbon atom number 5~15₂,-O- or-CO-, a and b separately indicate 0~4 Integer,

R³~R⁶Separately indicate the alkyl of hydrogen atom, halogen atom or carbon atom number 1~6, the alkane of carbon atom number 1~6 The aryl of oxygroup or carbon atom number 6~12, Y indicate singly-bound, contain aliphatic or aromatic organic residue, and n is average repeats Number.]

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

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

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

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

[6] polycarbonate-based resin composition according to any one of above-mentioned [1]~[5], wherein relative to (A) Total 100 mass parts of ingredient and (B) ingredient also contain 0.1~1 mass parts of mixed powder of (C) containing polytetrafluoroethylene (PTFE).

[7] polycarbonate-based resin composition according to any one of above-mentioned [1]~[6], wherein relative to (A) Total 100 mass parts of ingredient and (B) ingredient also contain 0.01~0.15 mass parts (D) be selected from organic sulfonic acid alkali metal salt and It is at least one kind of in the alkali salt of organic sulfonic acid.

[8] a kind of formed products, it includes the polycarbonate-based resin compositions described in any one of above-mentioned [1]~[7].

[9] a kind of elec-tric-electronic sets spare unit, and it includes polycarbonate-based described in any one of above-mentioned [1]~[7] Resin combination.

[10] a kind of automotive part, it includes the polycarbonate-based resin combinations described in any one of above-mentioned [1]~[7] Object.

Invention effect

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

Specific embodiment

[polycarbonate-based resin composition]

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

(A) polycarbonate-based resin includes:

[changing 2]

In logical formula (I), as R¹And R²The halogen atom separately indicated can be enumerated: fluorine atom, chlorine atom, bromine are former Son, iodine atom.

As R¹And R²The alkyl separately indicated can be enumerated: methyl, ethyl, n-propyl, isopropyl, various butyl (it is " various " to indicate the group including straight-chain and all branched, there is same meaning below.), it is various amyls, various Hexyl.As R¹And R²The alkoxy separately indicated can enumerate the case where alkyl portion is the alkyl.

As the alkylidene that X is indicated, can enumerate for example: methylene, ethylidene, trimethylene, tetramethylene, hexa-methylene Deng the preferably alkylidene of carbon atom number 1~5.As the alkylidene radical that X is indicated, can enumerate: ethidine, isopropylidene etc..As The ring alkylidene that X is indicated, can enumerate: penta diyl of ring, hexamethylene diyl, the pungent diyl of ring etc., and the preferably ring of carbon atom number 5~10 is sub- Alkyl.As the ring alkylidene radical that X is indicated, can enumerate for example: cyclohexylidene base, 3,5,5- 3-methyl cyclohexanols pitch base, 2- adamantylidene The ring alkylidene radical of base etc., preferably the ring alkylidene radical of carbon atom number 5~10, more preferably carbon atom number 5~8.

A and b separately indicates 0~4 integer, preferably 0~2, more preferably 0 or 1.

In logical formula (II), as R³~R⁶The halogen atom separately indicated can be enumerated: fluorine atom, chlorine atom, bromine are former Son, iodine atom.As R³~R⁶Alkyl, the alkoxy separately indicated, can enumerate and R¹And R²The case where identical base Group.As R³~R⁶The aryl separately indicated can be enumerated: phenyl, naphthalene etc..

What it is as Y expression includes aliphatic organic residue, can be enumerated for example: 1~10 (preferably carbon atom of carbon atom number Number 1~6, more preferably carbon atom number 1~3) alkylidene etc..In addition, as Y indicate include aromatic organic residue, It can enumerate for example: arlydene of ring carbons numbers 6~12 such as phenylene, naphthylene, biphenyl diyl etc..

((A) polycarbonate-based resin)

-(A-1)-

It is carried out first to one of (A) ingredient and for " polycarbonate-poly organo alkyl copolymer (A-1) " of neccessary composition Explanation.

In polycarbonate-poly organo alkyl copolymer (A-1), the content of Component units shown in above-mentioned logical formula (II) is 2~20 mass %, preferably 2~15 mass %, more preferably 2~10 mass %, 3~8 mass % are more preferably, is further excellent It is selected as 4~7 mass %, particularly preferably 4~6 mass %.If the effect that impact resistant strength improves is not filled less than 2 mass % Point, if in addition more than 20 mass %, the reduction of heat resistance increases.

In addition, the averaged repeating numbers n in Component units shown in above-mentioned logical formula (II) is 25~65, is preferably in (A-1) 30~60,30~50, further preferably 30~45 are more preferably.(A-1) in, if n less than 25, impact resistant strength improve Effect is insufficient, if being difficult to obtain excellent color appearance more than 65.

(A-1) viscosity average molecular weigh (Mv) is preferably 16,000~30,000, more preferably 16,000~25,000, into one Step preferably 17,000~23,000.If the viscosity average molecular weigh of (A-1) is in the range, the intensity of formed products is abundant, copolymerization The viscosity of object will not become excessive, and productivity when manufacture is stablized, and also be easy to carry out thin molded.

Polycarbonate-poly organo alkyl copolymer (A-1) can by make divalent phenol shown in the following general formula (1), Polysiloxane shown in the following general formula (2) is copolymerized with phosgene, carbonic ester or chloro-formate to manufacture.In addition, by making Polycarbonate oligomer (such as the polycarbonate oligomer of end with chloro-carbonic acid ester group) is reacted with polysiloxane, Polycarbonate-poly organo alkyl copolymer (A-1) can also be produced.

In the manufacture of polycarbonate-poly organo alkyl copolymer (A-1), preferably making to gather shown in the following general formula (2) has The reactivity of organic siloxane is 95% or more, more preferably make its 97% or more, further preferably make its 99% or more.

[changing 3]

[in general formula (1), X, R¹~R², a and b it is identical as the situation in the logical formula (I).In general formula (2), R³~R⁶, Y and N is identical as the situation in the logical formula (II), and at manufacture (A-1), n is 25~65.Z indicates halogen atom ,-R⁷OH、-R⁷-Z′- R⁸-OH、-R⁷COOH、-R⁷NH₂,-COOH or-SH, the R⁷Indicate substituted or unsubstituted alkylidene, substituted or unsubstituted ring Alkylidene or substituted or unsubstituted arlydene.The R⁸Indicate the arlydene of ring carbons number 6~12, the Z ' expression The alkylidene of carbon atom number 1~8, the alkylidene radical of carbon atom number 2~8, the ring alkylidene of carbon atom number 5~10, carbon atom number 5~ 10 ring alkylidene radical.M indicates 0 or 1.]

As the halogen atom that Z is indicated, can enumerate for example: fluorine atom, chlorine atom, bromine atom, iodine atom.Among them preferably For chlorine atom.

- the R indicated as Z⁷OH、-R⁷-Z′-R⁸-OH、-R⁷COOH、-R⁷NH₂In R⁷The alkylidene of expression can enumerate example Such as: methylene, ethylidene, propylidene, trimethylene, pentamethylene carbon atom number 1~10 (preferably 1~5) alkylidene. In addition, as R⁷The ring alkylidene of expression, can enumerate for example: the ring carbons numbers 3~10 such as cyclopentylene, cyclohexylidene are (excellent Be selected as 4~8) ring alkylidene.As R⁷The arlydene of expression can be enumerated for example: phenylene, naphthylene, biphenyl diyl etc. at The arlydene of ring carbon atom number 6~12.

R⁷Can by the alkyl of carbon atom number 1~5, the alkoxy of carbon atom number 1~5, ring carbons number 6~12 virtue Base etc. replaces.It as the alkyl, can enumerate: methyl, ethyl, propyl, various butyl etc..As the alkoxy, can enumerate: alkyl Position is the group of the alkyl.As the aryl, phenyl etc. can be enumerated.

As the alkylidene of Z ' expression, alkylidene radical, ring alkylidene, ring alkylidene radical, the case where can enumerating with X identical base Group.As Z ', the preferably alkylidene radical of carbon atom number 2~8, more preferably isopropylidene.

-(A-2)-

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

In polycarbonate-poly organo alkyl copolymer (A-2), the content of Component units shown in the logical formula (II) is It 2~20 mass %, preferably 2~15 mass %, more preferably 2~10 mass %, is more preferably 3~8 mass %, special Preferably 3~7 mass %.If the effect that impact resistant strength improves is insufficient, if in addition more than 20 matter less than 2 mass % % is measured, then the reduction of heat resistance increases.

In addition, the averaged repeating numbers n in Component units shown in above-mentioned logical formula (II) is 70~350, preferably in (A-2) It is 80~200, more preferably 80~110, further preferably 80~100.If n is less than 70, the effect of impact resistant strength raising Fruit is insufficient, if viscosity increases more than 350, operability is deteriorated.

(A-2) viscosity average molecular weigh (Mv) is preferably 16,000~30,000, more preferably 16,000~25,000, into one Step preferably 17,000~23,000.If the viscosity average molecular weigh of (A-2) is in the range, the intensity of formed products is abundant, copolymerization The viscosity of object will not become excessive, and productivity when manufacture is stablized, and also be easy to carry out thin molded.

Further, from the generation for the bad order for inhibiting blackstreak, it is easily obtained the effect for improving impact resistant strength Viewpoint is set out, and Component units shown in the logical formula (II) in (A-2) are preferably 2.5 mass % relative to (A) ingredient total amount Below, 2.0 mass % or less are more preferably.

Polycarbonate-poly organo alkyl copolymer (A-2) can by make divalent phenol shown in the general formula (1), Polysiloxane shown in the general formula (2) (wherein, n is 70~350) is copolymerized with phosgene, carbonic ester or chloro-formate To manufacture.In addition, by making polycarbonate oligomer (such as the polycarbonate oligomer of end with chloro-carbonic acid ester group) and gathering Organosiloxane is reacted, and polycarbonate-poly organo alkyl copolymer (A-2) can also be produced.

In the manufacture of polycarbonate-poly organo alkyl copolymer (A-2), preferably making to gather shown in the general formula (2) has The reactivity of organic siloxane is 90% or more, more preferably make its 95% or more, further preferably make its 97% or more, especially It is preferred that make its 99% or more.

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

It as the bis-phenol other than bisphenol-A, can enumerate for example: bis- (4- hydroxy phenyl) methane, 1,1- bis- (4- hydroxy phenyls) It is bis- (4- hydroxy phenyl) butane of ethane, 2,2-, bis- (4- hydroxy phenyl) octanes of 2,2-, bis- (4- hydroxy phenyl) phenylmethanes, double Bis- (the 4- hydroxy-3-methyl phenyl) propane of (4- hydroxy phenyl) diphenyl methane, 2,2-, bis- (4- hydroxy phenyl) naphthyl methanes, Bis- (4- hydroxyl -3- bromophenyl) propane of 1,1- bis- (4- hydroxytertiarybutylphenyl) propane, 2,2-, bis- (the 4- hydroxyls -3,5- tetra- of 2,2- Aminomethyl phenyl) propane, bis- (4- hydroxyl -3- chlorphenyl) propane of 2,2-, 2,2- bis- (4- hydroxyl -3,5- dichlorophenyl) propane, 2, Bis- (hydroxyaryl) alkanes such as bis- (4- hydroxyl -3, the 5- dibromo phenyl) propane of 2-；1,1- bis- (4- hydroxy phenyl) pentamethylene, 1, Bis- (the 4- hydroxy phenyls) -3 of 1- bis(4-hydroxyphenyl)cyclohexane, 1,1-, bis- (the 4- hydroxy benzenes of 5,5- trimethyl-cyclohexanes, 2,2- Base) bis- (hydroxyaryl) cycloalkanes such as norbornane, bis- (4- hydroxy phenyl) cyclododecanes of 1,1-；4,4 '-dihydroxy phenyls Ether, 4,4 '-dihydroxy -3, the dihydroxy aryl ethers such as 3 ' -3,5-dimethylphenyl ethers；4,4 '-dihydroxydiphenyl thioethers, 4,4 '- The dihydroxy diaryls thioether classes such as 3,3 '-dimethyl diphenyl sulfide of dihydroxy-；4,4 '-dihydroxydiphenyl sulfoxides, 4,4 '- The dihydroxy diaryls sulfoxide types such as 3,3 '-dimethyl diphenyl sulfoxide of dihydroxy-；4,4 '-dihydroxy-diphenyl sulfones, 4,4 '-two The dihydroxy diaryls sulfone classes such as 3,3 '-dimethyl diphenyl sulfone of hydroxyl-；The dihydroxybiphenyls classes such as 4,4 '-dihydroxybiphenyls；9,9- The dihydroxy diaryls fluorenes classes such as bis- (the 4- hydroxy-3-methyl phenyl) fluorenes of bis- (4- hydroxy phenyl) fluorenes, 9,9-；Bis- (4- hydroxy phenyls) Bis- (4- hydroxy phenyl) adamantane of diphenyl methane, 1,3-, bis- (4- hydroxy phenyl) adamantane of 2,2-, bis- (the 4- hydroxy benzenes of 1,3- Base) the dihydroxy diaryls adamantane such as -5,7- dimethyladamantane；4,4 '-[1,3- phenylene is bis- (1- methyl ethidine)] Bis- (4- hydroxy benzenes sulfenyl) -2,3- dioxole of bis- (4- the hydroxy phenyl) -9- anthrones of bis-phenol, 10,10-, 1,5- etc..

These divalent phenols can be used alone, and can also be mixed with two or more.

Polysiloxane shown in general formula (2) can be by the preferred second of phenols that makes to have olefinic unsaturation carbon-carbon bond Alkenyl phenol, chavicol, eugenol, isopropenyl phenol etc. are in the polysiloxane chain with regulation polymerization degree n End occur hydrosilylation (hydrosilanation) reaction and be easily manufactured.Above-mentioned phenol is more preferably allyl Base phenol or eugenol.At this point, (A-1), (A-2) logical formula (II) in Y be from chavicol or eugenol Organic residue.

As polysiloxane shown in general formula (2), polysiloxane for example below can be enumerated.

[changing 4]

In general formula (3)~(11), R³~R⁶With the R in general formula (1)³~R⁶Equally.N is that organosiloxane constitutes list The averaged repeating numbers of member indicate 25~65 in the case where (A-1), 70~350 are indicated in the case where (A-2).In addition, c is indicated just Integer, preferably 1~6 integer, more preferably 1~3 integer, further preferably 3.

Wherein, from the viewpoint of polymerizeing easiness, phenol modified polyorganosiloxanes (preferably c shown in preferred formula (3) =3).α, ω-from the viewpoint of accessibility, further preferably as one of general formula (4) compound represented Bis- [3- (o-hydroxy-phenyl) propyl] dimethyl silicone polymers or the α as one of general formula (5) compound represented, Bis- [3- (the 4- hydroxy 3-methoxybenzene base) propyl] dimethyl silicone polymers of ω-.

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

It reacts cyclotrisiloxane and disiloxane in the presence of acidic, synthesizes α, the organic poly- silicon oxygen of ω-dihydro Alkane.At this point, the α with desired repetitive unit can be synthesized by the feed ratio for changing cyclotrisiloxane and disiloxane, ω-dihydro organopolysiloxane.Then, in the presence of hydrosilylation reactions catalyst, make the chavicol, Ding Zi Fragrant phenol etc. has the phenolic compounds and α of unsaturated fatty hydrocarbons base, and addition reaction occurs for ω-dihydro organopolysiloxane, thus The phenol modified polyorganosiloxanes with desired repetitive unit can be manufactured.

In addition, in this stage, the cyclic polyorganosiloxane of low molecular weight, excessive above-mentioned phenolic compounds are with impurity Form residual, therefore heat under reduced pressure, these low molecular compounds are distilled off.

-(A-3)-

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

(A-3) the whole aromatic copolycarbonates being equivalent to other than (A-1) and (A-2).Wherein, as (A-3), preferably Aromatic copolycarbonate only comprising Component units shown in the logical formula (I).

In polycarbonate-based resin composition of the invention, (A-3), which can be used, utilizes previous aromatic copolycarbonate The obtained aromatic copolycarbonate of autofrettage, that is, make divalent benzene in the presence of the organic solvent of reactionlessness, aqueous alkali After phenol system compound and phosgene reaction, adds the polymerization catalysts such as tertiary amine or quaternary ammonium salt and make the interfacial polymerization of its polymerization； It is dissolved to divalent phenol based compound in the mixed solution of pyridine or pyridine and atent solvent, imports phosgene and directly manufacture Pyridine method etc..

It, can be as needed using end terminator, molecular weight regulator, branching agent etc. in above-mentioned reaction.

Divalent phenol system compound used in manufacture as (A-3), can enumerate bis- (4- hydroxy phenyl) propane of 2,2- (= Bisphenol-A), bis- (4- hydroxy phenyl) methane, bis- (4- hydroxy phenyl) ethane of 1,1-, 2,2- bis- (4- hydroxy phenyl) butane, 2,2- Bis- (4- hydroxy phenyl) octanes, bis- (4- hydroxy phenyl) phenylmethanes, bis- (4- hydroxy phenyl) diphenyl methanes, the bis- (4- of 2,2- Hydroxy-3-methyl phenyl) propane, bis- (4- hydroxy phenyl) naphthyl methanes, bis- (4- hydroxyl -3- tert-butyl-phenyl) propane of 1,1-, 2,2- bis- (4- hydroxyl -3- bromophenyl) propane, bis- (4- hydroxyl -3, the 5- 3,5-dimethylphenyl) propane of 2,2-, bis- (the 4- hydroxyls-of 2,2- 3- chlorphenyl) propane, bis- (4- hydroxyl -3, the 5- dichlorophenyl) propane of 2,2-, bis- (4- hydroxyl -3, the 5- dibromo phenyl) propane of 2,2- Deng bis- (hydroxyaryl) alkanes；1,1- bis- (4- hydroxy phenyl) pentamethylene, 1,1- bis(4-hydroxyphenyl)cyclohexane, 1,1- are bis- (4- hydroxy phenyl) -3, bis- (4- hydroxy phenyl) norbornanes of 5,5- trimethyl-cyclohexanes, 2,2-, 1,1- bis- (4- hydroxy phenyls) Bis- (hydroxyaryl) cycloalkanes such as cyclododecane；4,4 '-dihydroxy phenyl ethers, 4,4 '-dihydroxy -3,3 ' -3,5-dimethylphenyls The dihydroxy aryl ethers such as ether；4,4 '-dihydroxydiphenyl thioethers, 4,4 '-dihydroxy -3,3 '-dimethyl diphenyl sulfides etc. Dihydroxy diaryl thioether class；4,4 '-dihydroxydiphenyl sulfoxides, 4,4 '-dihydroxy -3,3 '-dimethyl diphenyl sulfoxides etc. Dihydroxy diaryl sulfoxide type；4,4 '-dihydroxy-diphenyl sulfones, 4,4 '-dihydroxy -3, the dihydroxies such as 3 '-dimethyl diphenyl sulfones Base diaryl sulfone class；The dihydroxybiphenyls classes such as 4,4 '-dihydroxybiphenyls；9,9- bis- (4- hydroxy phenyl) fluorenes, bis- (the 4- hydroxyls of 9,9- Base -3- aminomethyl phenyl) the dihydroxy diaryls fluorenes class such as fluorenes；Bis- (4- hydroxy phenyl) diphenyl methanes, bis- (the 4- hydroxy benzenes of 1,3- Base) dihydroxies such as adamantane, bis- (4- hydroxy phenyl) adamantane of 2,2-, bis- (4- hydroxy phenyl) -5, the 7- dimethyladamantanes of 1,3- Base diaryl adamantane；4,4 '-[1,3- phenylene is bis- (1- methyl ethidine)] bis-phenols, 10,10- bis- (4- hydroxy phenyls)- Bis- (4- hydroxy benzenes sulfenyl) -2,3- dioxa amylenes of 9- anthrone, 1,5- etc..These divalent phenols can use individually, It can be used in mixed way two or more.

In the manufacture of (A-3), usually using end terminator or molecular weight regulator.

As molecular weight regulator, as long as being that typically in molecular weight regulator used in the polymerization of polycarbonate resin, Various substances then can be used.

Specifically, as a bivalent phenol, it can be mentioned, for example: phenol, adjacent normal-butyl phenol, normal-butyl phenol, to just Butylphenol, adjacent isobutyl group phenol, isobutyl group phenol, to isobutyl group phenol, o-tert-butylphenol, tert-butyl phenol, right Tert-butyl phenol, adjacent n-pentyl phenol, n-pentyl phenol, to n-pentyl phenol, adjacent n-hexyl phenol, n-hexyl phenol, To n-hexyl phenol, to tert-octyl phenol, o cyclohexyl phenol, cyclohexylphenol, p-cyclohexylphenol, o-phenyl phenol, Between phenylphenol, p-phenyl phenol, adjacent n-nonyl phenol, nonyl phenol, to n-nonyl phenol, adjacent cumyl phenol, cumyl Phenol, p -cumylphenol, adjacent naphthalene phenol, naphthalene phenol, to naphthalene phenol, 2,5- DI-tert-butylphenol compounds, the tertiary fourth of 2,4- bis- Base phenol, 3,5- DI-tert-butylphenol compounds, 2,5- dicumyl phenol, 3,5- dicumyl phenol, paracresol, bromophenol, tribromphenol, Ortho position, meta or para position have average carbon atom number be 12~35 straight-chain 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..

, it is preferable to use p-tert-butylphenol, p -cumylphenol, p-phenyl phenol etc. in these bivalent phenols.Certainly also Two or more compounds can be used together.

It further, can be by 0.01~3 mole of %, particularly 0.1~1 relative to above-mentioned divalent phenol based compound The range of mole % and with branching agent, forming branching polycarbonate as branching agent can be used 1,1,1- tri- (4- hydroxy benzenes Base) ethane, 4,4 '-[1- [4- [1- (4- hydroxy phenyl) -1- Methylethyl] phenyl] ethidine] bis-phenols, α, (the 4- of α ', α "-three Hydroxy phenyl) -1,3,5- triisopropylbenzenes, 1- [Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl] -4- [α ', α '-bis- (4 "-hydroxyls Phenyl) ethyl] benzene, phloroglucin (Off ロログリシ Application), trimellitic acid, isatin bis- (o-cresols) etc. have 3 or more functions The compound of group.

(compounding ratio of each (A) ingredient)

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

If the content of (A-1) in (A) ingredient less than 5 mass %, needs to make containing logical formula (II) at manufacture (A-1) Shown in structural unit polysiloxane block section content be 20 mass % or more, in this case, in manufacture (A- 1) uniformity reacted in polymerization process when reduces sometimes, and polymer and ejected wash water in the cleaning process of polymer Separation property be deteriorated sometimes, therefore the productivity of (A-1) substantially reduces.On the other hand, if the content of (A-2), (A-3) are more than 95 mass % then since the ratio of (A-1) is less than 5 mass %, thus need to increase at manufacture (A-1) containing logical formula (II) institute The content of the polysiloxane block section of the structural unit shown, for as described above the reasons why without preferred.

From viewpoint similar to the above, the content of (A-1) in (A) ingredient is preferably 20~100 mass %, more excellent 30~100 mass %, further preferably 40~100 mass % are selected as, the content of (A-2) is preferably 0~80 mass %, more excellent It is preferred to be selected as 0~70 mass %, further preferably 0~60 mass %, particularly preferably 0~40 mass %, the content of (A-3) For 0~80 mass %, more preferably 0~70 mass %, further preferably 0~60 mass %, particularly preferably 0~40 matter Measure %.

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

(A) in the case that ingredient only contains (A-1) and (A-3), the containing ratio of the two is preferably (A-1) 20~95 matter % and (A-3) 80~5 mass % is measured, (A-1) 20~90 mass % and (A-3) 80~10 mass % is more preferably, is further excellent It is selected as (A-1) 50~90 mass % and (A-3) 50~10 mass %.

In addition, their containing ratio is preferably (A-1) in the case that (A) ingredient contains the whole of (A-1)~(A-3) 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 polycarbonate-based resin composition of the invention, from the viewpoint of impact resistant strength, (B) titanium oxide (dioxy Change titanium: TiO₂) content relative to (A) 99.9~96 mass parts be 0.1~4 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) at Point and (B) ingredient add up to 100 mass parts.).

Average grain diameter of titanium oxide is preferably 0.05~0.5 μm, more preferably 0.1~0.4 μm, is 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 aluminium, silicon, magnesium, oxidation The hydrous oxide and/or oxide of at least one element of the elements such as zirconium, titanium, tin coat.Titanium oxide can be further by not Polyalcohol, organo-silicon compound, ethyl alcohol amine, higher aliphatic acids of nitrogen atom etc. are surface-treated.As titanium oxide, It is preferred that being coated by aluminium, the hydrous oxide of silicon and/or oxide.In addition, it is also preferred that carrying out table by the polyalcohol of not nitrogen atom Titanium oxide after surface treatment.

It as the polyalcohol of the not nitrogen atom for coating titanium oxide, can enumerate: trimethylolpropane, trihydroxy methyl second Alkane, double trimethylolpropane, trimethylolpropane ethoxylate, pentaerythrite etc., wherein from can prevent impact strength from dropping From the perspective of low, preferably trimethylolpropane and trimethylolethane.These polyalcohols can be used alone, can also be with Two or more is applied in combination.

It can be any one in damp process and dry method with the method for the polyalcohol clad surface of not nitrogen atom. Damp process can carry out by the following method: oxidation being added in the polyalcohol of not nitrogen atom and the mixed liquor of low boiling point solvent Low boiling point solvent is removed after titanium, stirring.Dry method can carry out by the following method: by the polyalcohol of not nitrogen atom and oxidation Titanium is mixed in enjoying the mixing machines such as She Er mixing machine, rotary drum, or by the dissolution of the polyalcohol of not nitrogen atom in a solvent, Or it is dispersed in mixed solution obtained in solvent and carries out spraying method to titanium oxide.

The manufacturing method of titanium oxide can be to utilize any one method manufactured in chlorine method, sulfuric acid process.In addition, Rutile-type, any one in Detitanium-ore-type can be used in the crystal structure of titanium oxide, but combines from polycarbonate-based resin The viewpoints such as the thermal stability of object and light resistance are set out, preferably rutile-type.

(mixed powder of (C) containing polytetrafluoroethylene (PTFE))

Polycarbonate-based resin composition of the invention can also further cooperate the mixed powder containing polytetrafluoroethylene (PTFE) As (C) ingredient.Mixed powder containing polytetrafluoroethylene (PTFE) include 10 μm of polytetrafluoroethylene (PTFE) system below particles of average grain diameter and Organic based polymer particle.

The form of mixed powder containing polytetrafluoroethylene (PTFE) is with polytetrafluoroethylene (PTFE) system particle and organic based polymer particle Mixing ratio, partial size and difference, are not particularly limited.Such as in the presence of: organic based polymer particle surrounds polytetrafluoroethylene (PTFE) system particle The form of surrounding, opposite to that ground polytetrafluoroethylene (PTFE) system particle surround organic based polymer particle surrounding form, multiple Form etc. of the particle relative to 1 particle coacervation.

Mixed powder used in the present invention containing polytetrafluoroethylene (PTFE) needs: including 10 μm of polytetrafluoroethyl-nes below of partial size Alkene particle and organic based polymer, and polytetrafluoroethylene (PTFE) does not become 10 μm or more of condensate in powder.Contain as such There is the mixed powder of polytetrafluoroethylene (PTFE), preferably: 0.05~1.0 μm of partial size of polytetrafluoroethylparticle particle aqueous liquid dispersion and organic system By solidifying or being spray-dried powder mixed powder obtained by or in grain after the mixing of polymer particle aqueous liquid dispersion It will lead to after the monomer polymerization for constituting organic based polymer in the presence of 0.05~1.0 μm of diameter of polytetrafluoroethylparticle particle aqueous liquid dispersion Supersolidification or spray drying and powder mixed powder obtained by or it is being mixed with 0.05~1.0 μm of partial size of polytetrafluoro It will be with ethylenic unsaturated bond in the dispersion liquid of beta particles aqueous liquid dispersion and organic based polymer particle aqueous liquid dispersion By solidifying or being spray-dried powder mixed powder obtained by after monomer emulsion polymerization.

In addition, 0.05~1.0 μm of partial size of polytetrafluoroethylparticle particle aqueous liquid dispersion can be by using fluorine-containing surfactants The emulsion polymerization of agent obtains tetrafluoroethylene monomer polymerization.When emulsion polymerization, copolymer composition is used as in polytetrafluoroethylene (PTFE), it can To use: the Fluorine containing olefines such as hexafluoropropene, chlorotrifluoroethylene, fluoroalkylvinyl, perfluoroalkyl vinyl ether, (methyl) propylene The fluorine-containing Arrcostab of sour perfluoroalkyl ester etc. (methyl) acrylic acid.These copolymer compositions are preferably 10 mass % relative to tetrafluoroethene Below.

As the marketable material of polytetrafluoroethylene (PTFE) system particle aqueous liquid dispersion, Asashi ICI can be enumerated The Fluon AD-1, AD-936, Polyflon D-1, the D-2 of Daikin Industries corporation of Fluoropolymer corporation, three wells Teflon (registered trademark) 30J of Du Pont's fluorine chemistry corporation etc. is as representative examples.

The organic based polymer particle is not particularly limited, and can enumerate for example: polycarbonate (PC), poly terephthalic acid Glycol ester, polybutylene terephthalate (PBT), polyethylene naphthalate, polybutylene naphthalate, 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, copolymer, phenolic resin, Lauxite, trimerization comprising aromatic series alkenyl compound Yu vinyl cyanide based compound Melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, 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 object, the hydride of the 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 copolymer, ethylene-methyl acrylate, Ethylene-butyl acrylate of alpha-olefin, Acrylate-butadiene copolymer, the acrylic flexible polymer such as butyl acrylate-butadiene, ethane-acetic acid ethyenyl The ethylene-propylenes such as copolymer, ethylene-propylene-ethylidene norbornene copolymer, the ethylene-propylene-hexadiene copolymer of ester are non- Conjugated diene terpolymer, butylene-isoprene copolymer, haloflex, polysiloxane, poly- (methyl) acrylic acid The rubber polymers such as Arrcostab, compounded rubber, rubber mass comprising polysiloxane and poly- (methyl) alkyl acrylate Graft copolymer made of polymer and aromatic vinyl monomer and cyanided vinyl monomer are graft-polymerized includes poly-organosilicon Compounded rubber graft copolymerization made of the compounded rubber and vinyl monomer-grafted of oxygen alkane and poly- (methyl) alkyl acrylate Object and contain the 50 mass % polymer below of ingredient etc. that can be copolymerized with them relative to whole polymer.These polymerizations Object can be used singly or in combination of two or more.

From the viewpoint of the dispersibility of polytetrafluoroethylene (PTFE), preferably with polycarbonate-based resin is affinity polymerize Object, particularly preferably using poly- (methyl) alkyl acrylate as the polymer of principal component, rubber polymer, further preferably 30 mass % or more have the polymer of poly- (methyl) alkyl acrylate of the alkyl of 4 or more carbon atom number.

As the rubber polymer, may be exemplified: polybutadiene, polyisoprene, styrene-butadiene it is random Copolymer and block copolymer, the hydride of the block copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene are total 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 copolymer, ethylene-methyl acrylate, the Ethylene-butyl acrylate of section copolymer, ethylene and alpha-olefin Copolymer, acrylate-butadiene copolymer, the acrylic acid series flexible polymer such as butyl acrylate-butadiene of carboxylate Object, the copolymer of ethane-acetic acid ethyenyl ester, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene are total The ethylene-propylenes non-conjugated diene such as polymers terpolymer, butylene-isoprene copolymer etc., these polymer can be independent It uses, two or more can also be applied in combination.

Wherein, ethylene-propylene rubber, ethylene-propylene non-conjugated diene terpolymer diene series rubber, third are preferably illustrated Olefin(e) acid system elastomeric polymer especially may be exemplified polybutadiene, styrene-butadiene copolymer, preferably polybutadiene, benzene second Alkene-butadiene copolymer, poly- (methyl) alkyl acrylate, includes polysiloxane and poly- (methyl) at polysiloxane The compounded rubber etc. of alkyl acrylate.As the autofrettage of these organic based polymers, bulk polymerization can be used, solution gathers The generally well-known method such as conjunction, suspension polymerisation, emulsion polymerization.

The mixing of polytetrafluoroethylene (PTFE) system particle and organic polymer particle in mixed powder containing polytetrafluoroethylene (PTFE) Ratio is not particularly limited, but preferably polytetrafluoroethylene system particle is 0.1~90 mass %.About mixed containing polytetrafluoroethylene (PTFE) Close powder, can be by the way that polytetrafluoroethylene (PTFE) system particle dispersion and organic polymer particle dispersion be stirred obtained by The method etc. that aqueous liquid dispersion is put into the hot water dissolved with metal salts such as calcium chloride, magnesium sulfate and saltoutd, solidified, by This is separated and recovered in the form of particle.

In the case where cooperating (C) ingredient in polycarbonate-based resin composition of the invention, use level is relative to (A) Total 100 mass parts of ingredient and (B) ingredient are 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, can also it cooperate in polycarbonate-based resin composition of the invention selected from organic sulphur It is at least one kind of as (D) ingredient in the alkali metal salt of acid and the alkali salt of organic sulfonic acid.

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

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

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

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

(C_cF_2c+1SO₃)_dM···(12)

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

Such as the metal salt recorded in Japanese Patent Publication 47-40445 bulletin belongs to these metal salts.

In the general formula (12), as perfluoroalkane sulfonate, such as perfluor methanesulfonic acid, perfluor ethanesulfonic acid, complete can be enumerated 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..It is especially excellent Choosing uses their sylvite.

In addition, alkyl sulfonic acid, benzene sulfonic acid, alkyl benzene sulphonate, diphenyl sulfonic acid, naphthalene sulfonic acids, 2,5- dichloro-benzenes sulphur can be enumerated Acid, 2,4,5- trichlorine benzene sulfonic acids, diphenyl sulfone -3- sulfonic acid, 3,3 '-disulfonic acid of diphenyl sulfone -, naphthalene trisulfonic acid and their fluorine take For alkali metal salt, the alkali salt etc. of the organic sulfonic acids such as object and polystyrolsulfon acid.

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

As the alkali metal salt and/or alkali salt of polystyrolsulfon acid, can enumerate shown in the following general formula (13) Aromatic vinyl base system resin containing sulfonate group.

[changing 5]

[in formula (13), X indicates sulfonate group, and m indicates 1~5 integer.Y indicates hydrogen atom or carbon atom number 1~10 Alkyl.N indicates mole fraction, is 0 < n≤1.]

Here, sulfonate group is the alkali metal salt and/or alkali salt of sulfonic acid, as metal, can enumerate sodium, potassium, Lithium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium etc..

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

The integer that m is 1~5, n are the relationship of 0 n≤1 <.

That is, sulfonate group (X) can be and replace entirely to aromatic rings, it also may include replacing to aromatic moiety or not taking Generation.

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

(other compositions)

In polycarbonate-based resin composition of the invention, as other compositions, the previous addition of cooperation can according to need Well known various additives class into polycarbonate-based resin composition.It as these other compositions, can enumerate for example: enhancing Material, filler, stabilizer, antioxidant, ultraviolet absorbing agent, antistatic agent, lubricant, release agent, dyestuff, pigment, its His fire retardant, impact resistance improvement elastomer etc..

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

Preferably cooperate phosphorus system stabilizer in polycarbonate-based resin composition of the invention.

Polycarbonate-based resin composition of the invention contains titanium oxide, but titanium oxide is added in polycarbonate-based resin When, it is sometimes found that polycarbonate-based resin is decomposed, the undesirable effect for reducing its molecular weight.Phosphorus system stabilizer can use up Possibly inhibit the undesirable effect.

Phosphorus system used in the present invention stabilizer can enumerate aromatic series phosphine compound and/or phosphoric acid based compound.

As aromatic series phosphine compound, can enumerate for example: triphenylphosphine, diphenyl butylphosphine, diphenyl octadecyl phosphine, Three (p-methylphenyl) phosphines, three (to nonyl phenyl) phosphines, three naphthalene 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.

In addition, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester etc. can be enumerated as phosphoric acid based compound.Specifically For, can enumerate: triphenyl phosphite, three (nonyl phenyl) phosphite esters, three (2,4- di-tert-butyl-phenyl) phosphite esters, Tridecyl phosphite, trioctylphosphite, three (octadecyl) phosphite esters, didecyl list phenyl phosphites, two Octyl list phenyl phosphites, diisopropyl list phenyl phosphites, diphenyl iso-octyl phosphite ester, diphenyl n-octyl are sub- Phosphate, monobutyl diphenylphosphite, single decyl diphenyl phosphite ester, single octyl diphenyl phosphite ester, bis- (2,6- Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphites, 2,2- di-2-ethylhexylphosphine oxide (4,6- di-tert-butyl-phenyl) octyl Asia Phosphate, bis- (nonyl phenyl) pentaerythritol diphosphites, bis- (2,4- di-t-butyl phenyl) pentaerythrite diphosphorous acids Ester, distearyl pentaerythrityl diphosphite, Tributyl phosphate ester, triethyl phosphate, trimethyl phosphate, triphenyl phosphorus Acid esters, diphenyl list neighbour biphenyl phosphate, dibutylphosphoric acid ester, dioctyl phosphate, diisopropyl phosphate, 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.

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

In the case where cooperating above-mentioned phosphorus system stabilizer, total 100 mass parts relative to (A) ingredient and (B) ingredient are preferred For 0.1~1 mass parts.

Polycarbonate-based resin composition of the invention can be by (A) ingredient by described in and (B) ingredient and according to need Additive kind cooperation, the mixing wanted obtain.

The cooperation and mixing can be by commonly used approaches, such as use ribbon blender (ribbon Blender), Henschel mixer (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. carries out.

It should be noted that heating temperature when being kneaded can be in usual 250~320 DEG C of range into selection.

It can be used in the forming of the polycarbonate-based resin composition of the invention obtained as described above known Various manufacturing process, such as: injection molding method, ejection compress moulding method, extrusion molding method, flowing forming process, compression moulding method, Vacuum forming process and foaming and molding method etc..

It should be noted that in this specification, preferred (including preferred range.) combination between technical solution is certain It, can will any preferred technical solution (including preferred range it is preferred that in all regulations.) combination.

Embodiment

The embodiment of the present invention is further illustrated.It should be noted that the present invention is not by any of these examples Limitation.It should be noted that viscosity average molecular weigh (Mv), unreacted PDMS amount, the reactivity of PDMS pass through side below in each example Method is found out.

(measuring methods of 1. viscosity average molecular weighs (Mv))

The limiting viscosity (η) of the dichloromethane solution at 20 DEG C is measured using Ubbelohde viscosity tube, and passes through following relationship Formula (Schnell formula) is calculated.

(η)=1.23 × 10^-5×Mv^0.83

(calculation methods of 2. unreacted PDMS amounts)

(i) polycarbonate obtained in each case-polydimethylsiloxanecopolymer copolymer 6g is dissolved in methylene chloride 50ml institute After adding acetone 50ml and n-hexane 150ml in the solution obtained and mixing, 30 minutes are stood.

(ii) using filter paper (No.5A) by filtering recycling filtrate, the filtrate concentration of recycling is solid, it measures resulting dry Gu the weight of object.Obtained dry substance is dissolved in deuterated chloroform, is carried out¹H-NMR measurement.From unreacted phenol modified poly- two The integrated value x of the proton (δ 6.7ppm) at the hydroxyl ortho position of methylsiloxane, the proton (δ 0.6ppm) for belonging to methene chain Integrated value y calculates the ratio z (%) of unreacted PDMS by following formula.

Y × 100 z=2 × x ÷

(iii) on the other hand, in addition prepare modified poly- added with phenol in polycarbonate-polydimethylsiloxanecopolymer copolymer The standard specimen of 150~2000ppm of dimethyl siloxane, carries out operation similar to the above, thus finds out z and unreacted PDMS amount The relational expression of (ppm ,=phenol modified dimethyl polysiloxane additive amount).

By the z found out in (ii) and the relational expression found out by (iii), calculate unreacted PDMS amount (ppm).

(calculation method of the reactivity of 3.PDMS)

The reactivity of PDMS is calculated according to following calculating formulas.

PDMS reactivity (quality %)=(1- unreacted PDMS amount (quality %) ÷ polydimethylsiloxaneresidue residue amount (matter Measure %)) × 100

<the synthesis example of synthesis example 1>polycarbonate oligomer

Add 2000 mass ppm's relative to the bisphenol-A to be dissolved later into the sodium hydrate aqueous solution of 5.6 mass % Sodium dithionite makes the concentration of bisphenol-A be 13.5 mass %, prepares the sodium hydroxide water of bisphenol-A in wherein dissolution bisphenol-A Solution.

Under the sodium hydrate aqueous solution 40L/hr of the bisphenol-A, the flow of methylene chloride 15L/hr, with the stream of 4.0kg/hr It measures to the tube-type reactor of internal diameter 6mm, pipe range 30m and is continuously passed through phosgene.Tube-type reactor has jacket portion, to collet In be passed through cooling water, the temperature of reaction solution is maintained at 40 DEG C or less.

It is 40L with baffle that the reaction solution for flowing out tube-type reactor, which is continuously imported into the internal volume with swept-back wing, In tank reactor, then 25 matter are added with the sodium hydrate aqueous solution of 2.8L/hr addition bisphenol-A, with 0.07L/hr thereto It measures % sodium hydrate aqueous solution, water is added with 17L/hr, 1 mass % aqueous triethylamine is added with 0.64L/hr, carry out anti- It answers.The reaction solution overflowed from tank reactor is continuously extracted out, by standing, water phase is separated off, collects methylene chloride phase.

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

It should be noted that using THF (tetrahydrofuran) as developing solvent, pass through GPC (column: TOSOH TSK-GEL MULTIPORE HXL-M (2)+Shodex KF801 (1), 40 DEG C of temperature, flow velocity 1.0ml/ minutes, detector: RI), with The form of standard polystyren conversion molecular weight (weight average molecular weight: Mw) measures weight average molecular weight (Mw).

<Production Example 1>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-1]

It is added in synthesis example 1 and manufactures in the 50L tank reactor for having baffle, slurry type stirring flabellum and cooling collet Polycarbonate oligomer solution 15L, methylene chloride 8.9L, dimethylsiloxy units averaged repeating numbers be 40 2- allyl Base phenol end modified dimethyl polysiloxane (PDMS-1) 307g and triethylamine 8.8mL, are added 6.4 wherein under stiring 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 that p-tert-butylphenol (PTBP) is added in the polymer fluid Solution obtained from methane 2.0L], the sodium hydrate aqueous solution of bisphenol-A [make bisphenol-A 1147g be dissolved in sodium hydroxide 581g with Sodium dithionite 2.3g is dissolved in solution obtained from aqueous solution obtained from water 8.5L], implement 50 minutes polymerization reactions. It is added for stirring 10 minutes, being then separated into the organic phase containing polycarbonate and contained after diluted methylene chloride 10L The bisphenol-A of amount and the water phase of sodium hydroxide, and isolate organic phase.

For the polycarbonate-polydimethylsiloxanecopolymer copolymer dichloromethane solution obtained in this way, successively held with 15 0.03mol/L sodium hydrate aqueous solution, the 0.2mol/L hydrochloric acid of product % is cleaned, then with pure water repeated washing until cleaning The electrical conductivity in water phase afterwards is 0.01 μ S/m or less.Polycarbonate-the Dimethicone Copolyol that will be obtained by cleaning The dichloromethane solution concentration of object crushes, by obtained thin slice under reduced pressure in 120 DEG C of dryings.

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-1) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 4.8 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 49.5, viscous Average molecular weight (Mv) is 18,600.In addition, the amount of unreacted PDMS-1 is 150ppm hereinafter, the reactivity of PDMS-1 is 99.5% or more.

<Production Example 2>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-2]

In Production Example 1, the terminal-modified PDMS of 2- chavicol for being 40 by the repeat number of dimethylsiloxy units (PDMS-1) usage amount is set as 256g, and PTBP 107g is used to be dissolved in solution obtained from methylene chloride 2.0L as to uncle The dichloromethane solution of butylphenol (PTBP), is equally operated in addition to this, manufactures polycarbonate-dimethyl silicone polymer Copolymer.

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-2) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 4.0 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 55.9, glues Average molecular weight (Mv) is 21,400.In addition, the amount of unreacted PDMS-1 is 150ppm or less, the reactivity of PDMS-1 is 99.5% or more.

<Production Example 3>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-3]

In Production Example 1, the terminal-modified PDMS of 2- chavicol for being 40 by the repeat number of dimethylsiloxy units (PDMS-1) usage amount is set as 384g, and PTBP 137g is used to be dissolved in solution obtained from methylene chloride 2.0L as to uncle The dichloromethane solution of butylphenol (PTBP), is equally operated in addition to this, manufactures polycarbonate-dimethyl silicone polymer Copolymer (SiPC-3).

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-3) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 6.1 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 47.5, glues Average molecular weight (Mv) is 17,700.In addition, the amount of unreacted PDMS-1 is 150ppm or less, the reactivity of PDMS-1 is 99.5% or more.

<Production Example 4>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-4]

In Production Example 3, instead of dimethylsiloxy units repeat number be 40 the terminal-modified PDMS of 2- chavicol (PDMS-1) the terminal-modified PDMS of 2- chavicol (PDMS-2) that the repeat number of dimethylsiloxy units is 52 is used, It is equally operated, is manufactured polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-4) in addition to this.

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-4) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 6.0 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 47.5, glues Average molecular weight (Mv) is 177,00.In addition, the amount of unreacted PDMS-2 is 150ppm or less, the reactivity of PDMS-2 is 99.5% or more.

<Production Example 5>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-5]

In Production Example 1, the terminal-modified PDMS of 2- chavicol for being 40 by the repeat number of dimethylsiloxy units (PDMS-1) usage amount is set as 768g, is equally operated in addition to this, and polycarbonate-Dimethicone Copolyol is manufactured Object (SiPC-5).

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-5) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 12 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 46.8, it is viscous Molecular weight (Mv) is 17,400.In addition, the reactivity that the amount of unreacted PDMS-1 is 200ppm, PDMS-1 be 99.5% with On.

<Production Example 6>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-6]

In Production Example 1, the terminal-modified PDMS (PDMS- of eugenol for being 40 by the repeat number of dimethylsiloxy units 1) usage amount is set as 256g, is equally operated in addition to this, and polycarbonate-polydimethylsiloxanecopolymer copolymer is manufactured (SiPC-6)。

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-6) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 4.7 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 49.5, glues Average molecular weight (Mv) is 18,600.In addition, the amount of unreacted PDMS-1 is 150ppm or less, the reactivity of PDMS-1 is 99.5% or more.

<Production Example 7>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-2) [SiPC-7]

In Production Example 2, instead of dimethylsiloxy units repeat number be 40 the terminal-modified PDMS of 2- chavicol (PDMS-1) 256g and use dimethylsiloxy units repeat number be 150 the terminal-modified PDMS of 2- chavicol (PDMS-3) 256g is equally operated in addition to this, is manufactured polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-7).

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-7) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 3.9 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 55.9, glues Average molecular weight (Mv) is 21,400.In addition, the amount of unreacted PDMS-3 is 150ppm or less, the reactivity of PDMS-3 is 99.5% or more.

<Production Example 8>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-3) [SiPC-8]

In Production Example 6, instead of dimethylsiloxy units repeat number be 150 the terminal-modified PDMS of 2- chavicol (PDMS-3) the terminal-modified PDMS of 2- chavicol (PDMS-4) that the repeat number of dimethylsiloxy units is 20 is used, It is equally operated, is manufactured polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-8) in addition to this.

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-8) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 4.1 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 55.4, glues Average molecular weight (Mv) is 21,200.In addition, the amount of unreacted PDMS-4 is 150ppm or less, the reactivity of PDMS-4 is 99.5% or more.

<Production Example 9>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-2) [SiPC-9],

In Production Example 6, instead of dimethylsiloxy units repeat number be 150 the terminal-modified PDMS of 2- chavicol (PDMS-3) the terminal-modified PDMS of 2- chavicol (PDMS-4) that the repeat number of dimethylsiloxy units is 90 is used, It is equally operated, is manufactured polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-9) in addition to this.

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-9) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 4.0 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 55.9, glues Average molecular weight (Mv) is 21,400.In addition, the amount of unreacted PDMS-4 is 150ppm or less, the reactivity of PDMS-4 is 99.5% or more.

<Production Example 10>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-2) [SiPC-10]

In Production Example 3, instead of dimethylsiloxy units repeat number be 40 the terminal-modified PDMS of 2- chavicol (PDMS-1) the terminal-modified PDMS of 2- chavicol (PDMS-4) that the repeat number of dimethylsiloxy units is 90 is used, It is equally operated, is manufactured polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-10) in addition to this.

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-10) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 6.0 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 47.5, glues Average molecular weight (Mv) is 17,700.The amount of unreacted PDMS-4 is 150ppm or less, the reactivity of PDMS-4 be 99.5% with On.

<Production Example 11>polycarbonate-polydimethylsiloxanecopolymer copolymer (A-2) [SiPC-11]

(synthesis of the polycarbonate oligomer containing PDMS)

Add 2000 mass ppm's relative to the bisphenol-A to be dissolved later into the sodium hydrate aqueous solution of 5.6 mass % Sodium dithionite makes the concentration of BPA be 13.5 mass % in wherein dissolution bisphenol-A, and the sodium hydroxide for 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 the bisphenol-A, The flow of phosgene 4.0Kg/hr is continuously passed through the tube-type reactor of internal diameter 6mm, pipe range 30m.Tube-type reactor has collet Part is passed through cooling water into collet, and the temperature of reaction solution is maintained at 40 DEG C or less.

The concentration of the polycarbonate oligomer obtained in this way is 400g/L, and chloro-carbonic acid ester group concentration is 0.75mol/L.Separately Outside, 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 for having baffle, slurry type stirring flabellum and cooling collet Carbonate oligomer solution 15L, methylene chloride 8.9L, p-tert-butylphenol (PTBP) dichloromethane solution [by PTBP 129g Be dissolved in solution obtained from methylene chloride 2.0L], triethylamine 8.8mL, under stiring wherein be added BPA sodium hydroxide Aqueous solution [makes bisphenol-A 1231g be dissolved in sodium hydroxide 675g and sodium dithionite 2.4g and is dissolved in water obtained from water 9.9L Solution obtained from solution], implement 60 minutes polymerization reactions.It is added and is used for diluted methylene chloride 10L, stir 10 minutes Afterwards, it is separated into the organic phase containing polycarbonate and the water phase containing excessive bisphenol-A and sodium hydroxide, and is isolated organic Phase.

Polycarbonate-polydimethylsiloxanecopolymer copolymer (SiPC-11) that aforesaid operations obtain is found out by NMR measurement Polydimethylsiloxaneresidue residue amount be 20 mass %, the viscosity number based on ISO1628-4 (1999) measurement be 49.5, it is viscous Molecular weight (Mv) is 18,600.The amount of unreacted PDMS-2 is 150ppm or less, the reactivity of PDMS-2 is 99.5% or more.

Cooperated according to the use level (unit: mass parts) recorded in table 1 for describing ingredient, uses band ventilation holeSingle axle extruding machine, obtain granulated pellet at 280 DEG C of resin temperature.

By obtained granulated pellet at 120 DEG C after drying 8 hours, using injection machine, in forming temperature 280 DEG C, injection moulding at 80 DEG C of mold temperature, obtain test film.Use the test film as obtained from granulated pellet or injection moulding Carry out measurement below.The results are shown in Table 1.

(1) Izod impact strength

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

(2) formed products appearance

With after drying machine predrying 5 hours at 120 DEG C, with following conditions by thickness 1.5mm, long 140mm, width 140mm Formed products carry out 10 injection mouldings, visually observe the color appearance on its surface, evaluated according to following evaluation criteria.

Zero: absolutely not observing brown~black striped in formed products surface

×: observe brown~black striped in formed products surface

(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 in the case where being equivalent to 1.5mm thickness.

[table 1]

[table 2]

Table 2

The annotation in Tables 1 and 2 is illustrated below.

* 1: the polycarbonate-polydimethylsiloxanecopolymer copolymer manufactured respectively in Production Example 1~11

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

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

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

* 5: " CR-63 " is (Ishihara Sangyo Kaisha, Ltd.'s system, right with silica-alumina 1% and dimethyl silscone 0.5% Titanium dioxide be surface-treated after substance, average grain diameter: 0.21 μm)

* 6: " CR-60-2 " (Ishihara Sangyo Kaisha, Ltd.'s system, the titanium oxide by polyalcohol cladding, average grain diameter: 0.21 μ m)、

* 7: " PC3 " (Ishihara Sangyo Kaisha, Ltd.'s system, rutile-type, surface oxygen amount: 10 μm of 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, ingredient；Potassium perfluor butane sulfonate, Mitsubishi Materials electronization are at Co. Ltd. system)

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

* 11: polydimethylsiloxaneresidue residue

As shown in Table 1, polycarbonate-based resin composition of the invention can maintain polycarbonate-polysiloxane While excellent characteristic (such as impact resistance under impact resistance, particularly low temperature) of copolymer with excellent color outside It sees.In addition, anti-flammability is also excellent in embodiment 12 and 14.

On the other hand, from the comparative example 1 and 3 in table 2 it is found that not containing the poly- carbon of (A-1) and (A-2) containing (A-3) Acid ester resin composition, the reduction of impact resistance, particularly the reduction of the impact resistance under low temperature (- 20 DEG C) are significant.In addition, From comparative example 2,4 and 6 it is found that not containing the polycarbonate-based resin composition of (A-1) that averaged repeating numbers n is 25~65, (A-2) even if that is 70~350 containing averaged repeating numbers n, color appearance is also deteriorated.It is found that containing (A- as shown in comparative example 5 2) low although can maintain higher by the impact resistance at 23 DEG C with the polycarbonate-based resin composition of (A-3) Impact resistance under warm (- 20 DEG C) significantly reduces.Further, it is found that titanium oxide as (B) ingredient as shown in comparative example 7 When content is excessive, in any situation in 23 DEG C and -20 DEG C, impact resistance is significantly reduced.

Industrial availability

The polycarbonate-based resin composition obtained through the invention can be widely applied to electric appliance-electronic equipment neck The various fields such as domain, automotive field.It especially can also be used as mobile phone, laptop, digital camera, video recorder, electronic work The case material of tool etc. utilizes.

Claims

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

(A) polycarbonate-based resin includes:

Polycarbonate -5~100 mass % of poly organo alkyl copolymer (A-1), polycarbonate-poly organo alkyl copolymer (A-2) 0~95 mass % and 0~40 mass % of aromatic copolycarbonate (A-3) in addition to (A-1) and (A-2),

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

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

In the polycarbonate-based resin of (A) ingredient, the content phase of Component units shown in the logical formula (II) from (A-2) ingredient For (A-1)~(A-3) ingredient total amount be 2.5 mass % hereinafter,

In formula, R¹And R²Separately indicate halogen atom, the alkyl of carbon atom number 1~6 or the alkoxy of carbon atom number 1~6, X Indicate singly-bound, the alkylidene of carbon atom number 1~8, the alkylidene radical of carbon atom number 2~8, carbon atom number 5~15 ring alkylidene, carbon Ring alkylidene radical ,-the S- ,-SO- ,-SO of atomicity 5~15₂,-O- or-CO-, a and b separately indicate 0~4 integer,

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

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

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

4. polycarbonate-based resin composition according to claim 1 or 2, wherein the composition shown in logical formula (II) is single In member, R³~R⁶It is methyl.

5. polycarbonate-based resin composition according to claim 1 or 2, wherein relative to (A) ingredient and (B) ingredient Total 100 mass parts also contain 0.1~1 mass parts of mixed powder of (C) containing polytetrafluoroethylene (PTFE).

6. polycarbonate-based resin composition according to claim 1 or 2, wherein

Total 100 mass parts relative to (A) ingredient and (B) ingredient also contain 0.01~0.15 mass parts (D) and are selected from organic sulphur It is at least one kind of in the alkali metal salt of acid and the alkali salt of organic sulfonic acid.

7. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-1), lead to formula (II) Shown in Component units content be 3~8 mass %.

8. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-1), lead to formula (II) In averaged repeating numbers n be 30~60.

9. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-1), lead to formula (II) In averaged repeating numbers n be 30~50.

10. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-1), lead to formula (II) In averaged repeating numbers n be 30~45.

11. polycarbonate-based resin composition according to claim 1 or 2, wherein the viscosity average molecular weigh of (A-1) It (Mv) is 16,000~30,000.

12. polycarbonate-based resin composition according to claim 1 or 2, wherein the viscosity average molecular weigh of (A-1) It (Mv) is 16,000~25,000.

13. polycarbonate-based resin composition according to claim 1 or 2, wherein the viscosity average molecular weigh of (A-1) It (Mv) is 17,000~23,000.

14. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-2), lead to formula (II) Shown in Component units content be 2~15 mass %.

15. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-2), lead to formula (II) Shown in Component units content be 2~10 mass %.

16. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-2), lead to formula (II) Shown in Component units content be 3~8 mass %.

17. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-2), lead to formula (II) In averaged repeating numbers n be 80~200.

18. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-2), lead to formula (II) In averaged repeating numbers n be 80~110.

19. polycarbonate-based resin composition according to claim 1 or 2, wherein in (A-2), lead to formula (II) In averaged repeating numbers n be 80~100.

20. polycarbonate-based resin composition according to claim 1 or 2, wherein the viscosity average molecular weigh of (A-2) It (Mv) is 16,000~30,000.

21. polycarbonate-based resin composition according to claim 1 or 2, wherein the viscosity average molecular weigh of (A-2) It (Mv) is 16,000~25,000.

22. polycarbonate-based resin composition according to claim 1 or 2, wherein the viscosity average molecular weigh of (A-2) It (Mv) is 17,000~23,000.

23. polycarbonate-based resin composition according to claim 1 or 2, wherein the logical formula (II) in (A-2) Shown in Component units relative to (A) the ingredient total amount be 2.0 mass % or less.

24. polycarbonate-based resin composition according to claim 1 or 2, wherein (A-3) is only by the general formula (I) Component units shown in are constituted.

25. polycarbonate-based resin composition according to claim 1 or 2, wherein (A) is by (A-1) and (A-2) It constitutes,

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

26. polycarbonate-based resin composition according to claim 1 or 2, wherein (A) is by (A-1) and (A-2) It constitutes,

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

27. polycarbonate-based resin composition according to claim 1 or 2, wherein (A) is by (A-1) and (A-3) It constitutes,

It and include (A-1) of 60~95 mass % and (A-3) of 40~5 mass %.

28. polycarbonate-based resin composition according to claim 1 or 2, wherein (A) is by (A-1) and (A-3) It constitutes,

It and include (A-1) of 60~90 mass % and (A-3) of 40~10 mass %.

29. polycarbonate-based resin composition according to claim 1 or 2, wherein (A) includes (A-1)~(A- 3),

It and include (A-3) of (A-1) of 20~80 mass %, (A-2) of 10~60 mass % and 10~40 mass %.

30. polycarbonate-based resin composition according to claim 1 or 2, wherein (A) includes (A-1)~(A- 3),

It and include (A-3) of (A-1) of 25~60 mass %, (A-2) of 10~50 mass % and 25~40 mass %.

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

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

33. polycarbonate-based resin composition according to claim 1 or 2, wherein the primary of the titanium oxide (B) is put down Equal partial size is 0.05~0.5 μm.

34. polycarbonate-based resin composition according to claim 1 or 2, wherein the primary of (B) titanium oxide is put down Equal partial size is 0.1~0.4 μm.

35. polycarbonate-based resin composition according to claim 1 or 2, wherein the primary of the titanium oxide (B) is put down Equal partial size is 0.15~0.3 μm.

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

37. polycarbonate-based resin composition according to claim 1 or 2, wherein the titanium oxide (B) is not by nitrogenous Polyalcohol, organo-silicon compound, alkanolamine, the higher fatty acids of atom are surface-treated.

38. polycarbonate-based resin composition according to claim 1 or 2, wherein the titanium oxide (B) is by titanium dioxide Silicon-aluminium oxide 1% and dimethyl silscone 0.5% are surface-treated.

39. polycarbonate-based resin composition according to claim 5, wherein relative to (A) the polycarbonate-based tree Total 100 mass parts of rouge and (B) titanium oxide, (C) containing 0.1~0.6 mass parts contains the mixed powder of polytetrafluoroethylene (PTFE).

40. polycarbonate-based resin composition according to claim 6, wherein relative to (A) the polycarbonate-based tree Total 100 mass parts of rouge and (B) titanium oxide, (D) containing 0.03~0.1 mass parts be selected from organic sulfonic acid alkali metal salt and It is at least one kind of in the alkali salt of organic sulfonic acid.

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

42. a kind of formed products, it includes the polycarbonate-based resin compositions described in any one of Claims 1 to 41.

43. a kind of elec-tric-electronic sets spare unit, it includes the polycarbonate-based trees described in any one of Claims 1 to 41 Oil/fat composition.

44. a kind of automotive part, it includes the polycarbonate-based resin compositions described in any one of Claims 1 to 41.