CN104812796A

CN104812796A - Polycarbonate resin, polycarbonate resin composition, and molded article

Info

Publication number: CN104812796A
Application number: CN201380061947.7A
Authority: CN
Inventors: 大和田贵纪; 菅浩一; 中山由美
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2012-11-30
Filing date: 2013-11-28
Publication date: 2015-07-29
Anticipated expiration: 2033-11-28
Also published as: CN104812796B; JP2014108981A; TWI600678B; WO2014084327A1; JP6163297B2; TW201428023A

Abstract

A polycarbonate resin having a melt tension MT g at 280 ℃, a polycarbonate resin composition comprising the same, and a molded article]Melt flow at 280 ℃ MVR [ cm ]³10 minutes]Satisfies the following equations (1) to (3). Formula (1): MT is more than or equal to (15.4/MVR) -1.3; formula (2): MT is less than or equal to (57.4/MVR) -1.3; formula (3): MT is more than or equal to 1.

Description

Polycarbonate resin, poly carbonate resin composition and products formed

Technical field

The present invention relates to polycarbonate resin, poly carbonate resin composition and products formed, owing to also keeping in high-shear region, shaping mobility and melting tension force improve described polycarbonate resin, anti-dropping is excellent, therefore do not need to cause the additives such as opaque PTFE.

Background technology

Generally speaking, the polycarbonate resin manufactured by dihydroxyphenyl propane etc. due to the transparency, thermotolerance, mechanical characteristics excellent, thus use in purposes widely.But, this polycarbonate resin has following shortcoming: when for purposes such as blow molding, extrusion molding, vacuum formings, usual melting tension force is low, therefore products formed generation uneven thickness, or hangs down (drawdown) and can not obtain gratifying products formed.

On the other hand, known to suppress molten drop and give flame retardant resistance and use the tetrafluoroethylene (PTFE) with fibril Forming ability, but the poor compatibility of PTFE and polycarbonate resin and become the opaque reason of products formed.

Therefore, under the condition not using PTFE, give anti-dropping as by improving melting tension force, and make the method for the excellents such as the transparency, flame retardant resistance and shaping mobility, studying and making in polycarbonate resin containing branched structure.

Such as, in patent documentation 1, in order to make, there is the excellent transparency and the resin combination of flame retardant resistance, disclose and more than 1.1mol% and for the scope of below 1.5mol%, there is the aromatic polycarbonate resin of branched structure and the aromatic copolycarbonate resin composition containing fire retardant with a rate, show the concrete example using trihydric phenol as branching agent.

In addition, in patent documentation 2, disclose in order to solve hang down cause shaping time the too high and problem that formability that is that produce reduces of uneven thickness, melt viscosity, and make the branched polycarbonate resin that the low branching agent content x of 0.05 ~ 0.5mol% and melting tension force y meets the relation represented by specific formula, show the concrete example using trihydric phenol as branching agent.

In addition, as patent documentation 3, disclose to improve thermostability, formability and hanging down property, and make the low branching agent content x of 0.1 ~ 0.7mol% and melting tension force y and meet relation represented by specific formula, and the N amount in resin is 0 ~ 20ppm, Cl amount is the branched polycarbonate resin of 0 ~ 200ppm, show the concrete example using trihydric phenol as branching agent.

In addition, in patent documentation 4, disclose to make the transparency and good forming ability and there is the material of high abrasion resistance, and make relative to dihydric phenol 1mol use 0.0001 ~ 0.05mol using four phenolic compound represented by specific formula as branching agent, and specific viscosity is the branched polycarbonate resin of the scope of 0.20 ~ 2.0.

In addition, as patent documentation 5, improve and the improved products formed of outward appearance, tone to be provided in the middle formabilities such as blow molding, and disclose the specific 4 yuan of phenol of use as branching agent, and low, limiting viscosity [η] that branching agent content is 0.01 ~ 0.4mol% are the branched polycarbonate resin in fact without crosslinking structure of 0.5 ~ 0.6 (deciliter/gram).

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2011-105862 publication

Patent documentation 2: Japanese Patent No. 3693462 publications

Patent documentation 3: Japanese Unexamined Patent Publication 2005-126477 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2001-261808 publication

Patent documentation 5: Japanese Patent No. 4473446 publications

Summary of the invention

The problem that invention will solve

But, even if the branching agent of the branching agent of use 3 officials energy, 4 officials' energy is as branching agent, do not obtain the polycarbonate resin in high-shear region with excellent shaping mobility yet.

Therefore, the object of the invention is to, be provided in high-shear region and also keep shaping mobility, even and if do not add the also excellent polycarbonate resin of the anti-dropping such as PTFE, poly carbonate resin composition, the products formed that manufactured by these.

For the means of dealing with problems

What the present inventor etc. furtherd investigate repeatedly found that, by making the polycarbonate resin of melting tension force and the specific relational expression of melt-flow sexual satisfaction, or by making 4 officials above branching agent content and viscosity-average molecular weight be specified range, above-mentioned problem can be solved.

That is, the present invention relates to following polycarbonate resin, poly carbonate resin composition and products formed.

1. a polycarbonate resin, the melting tension force MT [g] when its 280 DEG C and melt fluidity MVR [cm when 280 DEG C ³/ 10 minutes] relation meet formula (1) ~ (3) below.

Formula (1): MT >=(15.4/MVR)-1.3

Formula (2): MT≤(57.4/MVR)-1.3

Formula (3): MT >=1

2. the polycarbonate resin according to above-mentioned 1, it comprises the polycarbonate resin with branched structure.

3. the polycarbonate resin according to above-mentioned 1, it comprises and has the polycarbonate resin of branched structure and the polycarbonate resin of straight-chain.

4. a polycarbonate resin, its viscosity-average molecular weight is 18,000 ~ 28, and 000,4 officials can branching agent content above be 0.5 ~ 2.0mol%.

5. a poly carbonate resin composition, it contains polycarbonate resin according to any one of above-mentioned 1 ~ 4 and additive.

6. the poly carbonate resin composition according to above-mentioned 5, wherein, described additive is fire retardant.

7. a products formed, it is by shaping for the poly carbonate resin composition described in the polycarbonate resin according to any one of above-mentioned 1 ~ 4 or above-mentioned 5 or 6.

8. the products formed according to above-mentioned 7, it is that blow molding forms.

Invention effect

According to the present invention, a kind of polycarbonate resin can be provided and comprise its poly carbonate resin composition, described polycarbonate resin is owing to also keeping shaping mobility in high-shear region, and melting tension force improves, anti-dropping is excellent, and does not need the PTFE etc. becoming opaque reason.

In addition, above-mentioned polycarbonate resin and the poly carbonate resin composition comprising it are particularly suitable for blow molding from above-mentioned characteristic, can provide above-mentioned polycarbonate resin and comprise the shaping products formed of its poly carbonate resin composition.

Accompanying drawing explanation

Fig. 1 represents melting tension force MT [g] in embodiment and comparative example and melt fluidity MVR [cm ³/ 10 minutes] the chart of relation (MT) × (1/MVR).

Embodiment

[physical property etc. of polycarbonate resin]

(melting tension force MT and melt fluidity MVR)

Polycarbonate resin of the present invention (following, sometimes referred to as " PC resin ".) 280 DEG C time melting tension force MT [g] with 280 DEG C time melt fluidity MVR [cm ³/ 10 minutes] relation meet formula (1) ~ (3) below.

Formula (1): MT >=(15.4/MVR)-1.3

Formula (2): MT≤(57.4/MVR)-1.3

Formula (3): MT >=1

By meeting formula (1) ~ (3) in the present invention, with existing PC resin-phase ratio, shaping mobility can be kept, and melting tension force improving, excellent anti-dropping can be guaranteed.

When not meeting formula (1), namely when MT < (15.4/MVR)-1.3, the anti-dropping of the excellence that the present invention plays can not be shown, in addition when not meeting formula (2), namely, when MT > (57.14/MVR)-1.3, good mobility can not be demonstrated in high shear force areas.In addition, can malsegregation be there is during polymerization, also be a problem at manufacture view.In addition, when not meeting formula (3), namely MT < 1 when can not guarantee sufficient anti-dropping, and the end of products formed rises and falls, or thickness produces deviation.

And then the relation of MT and MVR is:

From the view point of anti-dropping, preferably meet MT >=(20.6/MVR)-2.1, MT≤(57.4/MVR)-1.3, MT >=1;

From the view point of anti-dropping and shaping time mobility, more preferably meet MT >=(20.6/MVR)-2.1, MT≤(57.4/MVR)-1.3, MT >=1,1/MVR≤0.3;

From the view point of anti-dropping and shaping time mobility, preferably meet MT >=(20.6/MVR)-2.1, MT≤(57.4/MVR)-1.3, MT >=1,1/MVR≤0.25 further.

Above-mentioned melting tension force MT [g] be with 280 DEG C, hole (orifice) footpath L/D=8/2.095mm, extrusion speed 10mm/ minute, pulling speed 3.1m/ minute measure the value obtained.In addition, above-mentioned melt fluidity MVR [cm ³/ 10 minutes] be with 280 DEG C, the melt-flow volume of time per unit that measures of load 2.16kg.

In order to the melting tension force MT and melt fluidity MVR that make PC resin meet above-mentioned formula (1) ~ (3), can by the adjustment branching agent content of PC resin described later, viscosity-average molecular weight and reaching.Such as, can adjust by improving branching agent content described later to improve melting tension force MT, melt fluidity MVR can be adjusted by the viscosity-average molecular weight of PC resin in addition.

(branching agent content)

PC resin of the present invention demonstrates good melting tension force, in addition, in order to meet above-mentioned formula (1) ~ (3), preferably has the PC resin of branched structure.

In order to have branched structure, branching agent is used to manufacture PC resin, but under the state keeping good mobility in high shear force areas, improve melting tension force, preferred use 4 official can above branching agent, 4 officials further in preferred PC resin can branching agent content above be 0.5 ~ 2.0mol%, are more preferably 0.5 ~ 1.5mol%.

If above-mentioned branching agent content is more than 0.5mol%, then can give sufficient melting tension force to PC resin, in addition, if below 2.0mol%, then there is not the crosslinked and risk of gelation in polymkeric substance, and there is good shock-resistance, and can not produce muddy on the surface of products formed, there is the excellent transparency.

It should be noted that, above-mentioned branching agent content refers in the present invention, in the entirety of PC resin contained come from 4 officials can the structural unit of above branching agent relative to the structural unit coming from dihydric phenol used as raw material, come from the structural unit of end-capping reagent, and come from 4 officials can the mol% of total mole number of structural unit of above branching agent, namely, 4 officials can above branching agent content (mol%)=[come from 4 officials can structural unit (mol)/[come from the structural unit (mol) of the structural unit (mol) of dihydric phenol+come from end-capping reagent+come from 4 officials can the structural unit (mol) of above branching agent] of above branching agent] × 100.

Above-mentioned each structural unit (mol) can be passed through ¹h-NMR measures.

In addition, PC resin of the present invention preferably has branched structure to meet formula (1) ~ (3) as described above, as this, there is the PC resin of branched structure, can be the PC resin be only made up of the PC resin with branched structure, also can be the PC resin be made up of the PC resin of the PC resin and straight-chain with branched structure.From the view point of having more excellent flame retardant resistance, preferably using 30 ~ 100 quality % to have the PC resin of branched structure, being more preferably the PC resin be not made up of the one kind or two or more PC resin with branched structure containing the PC resin of straight-chain.

When multiple PC mixed with resin is made PC resin of the present invention, meet formula (1) ~ (3) as PC resin entirety, above-mentioned preferable range is become for branching agent content contained in above-mentioned branching agent content similarly PC resin entirety.The method of mixing can mix after manufacturing each PC resin for mixing, and the stage that also can be in molten state at each PC resin mixes, and is not particularly limited.

(viscosity-average molecular weight)

The viscosity-average molecular weight (Mv) of PC resin of the present invention is preferably 18,000 ~ 28,000, is more preferably 20,000 ~ 25,000.

If viscosity-average molecular weight is 18, more than 000, then anti-dropping becomes abundant and can embody good flame retardant resistance, thus preferably.If viscosity-average molecular weight is 28, less than 000 in addition, then set out preferably in the risk that the MVR that never there is PC resin becomes too low and has problems when shaping.

In the present invention, viscosity-average molecular weight (Mv) is by using Ubbelohde viscometer, and the viscosity of dichloromethane solution when measuring 20 DEG C, is obtained limiting viscosity [η] thus, calculated by formula below.

[η]＝1.23×10 ^-5Mv ^0.83

In addition, the invention provides 4 officials can branching agent content be above 0.5 ~ 2.0mol%, viscosity-average molecular weight is 18,000 ~ 28, the PC resin of 000.

By making 4 officials above branching agent content and viscosity-average molecular weight be above-mentioned scope, the PC resin of anti-dropping excellence can be made.Can above branching agent content and viscosity-average molecular weight be in the PC resin of above-mentioned scope 4 officials, if above-mentioned branching agent content is outside the scope of 0.5 ~ 2.0mol%, then can not give sufficient melting tension force to PC resin, good mobility can not be kept in high shear force areas.In addition, likely crosslinked polymer and gelation, shock-resistance and the transparency reduce.Above-mentioned branching agent content is preferably 0.5 ~ 1.5mol%.In addition, if above-mentioned viscosity-average molecular weight is 18,000 ~ 28, outside the scope of 000, then anti-dropping becomes insufficient, shaping become difficulty.Above-mentioned viscosity-average molecular weight is preferably 20, and 000 ~ 25,000.

It should be noted that, herein indication 4 officials can above branching agent content identical with the descriptive sense in the PC resin meeting formula (1) ~ (3) at above-mentioned MT and MVR with viscosity-average molecular weight.

Further, above-mentioned 4 officials can above branching agent content and viscosity-average molecular weight be the PC resin of above-mentioned scope can be the PC resins be only made up of the PC resin with branched structure, also can be the PC resins be made up of the PC resin of the PC resin and straight-chain with branched structure.Be preferably the PC resin be not made up of the one kind or two or more PC resin with branched structure containing the PC resin of straight-chain.

In addition, above-mentioned 4 officials can above branching agent content and viscosity-average molecular weight be formula (1) ~ (3) that the PC resin of above-mentioned scope preferably meets the relation of MT and the MVR representing above-mentioned, and the preferred version of the relation of MT and MVR is also same as above.

[raw material of polycarbonate resin]

PC resin of the present invention can be aromatic series PC resin also can be aliphatics PC resin, but from the view point of shock-resistance and thermotolerance, is preferably aromatic series PC resin.Aromatic series PC resin in the present invention preferably can use branching agent, dihydric phenol and end-capping reagent to manufacture.In addition, its manufacture method is not particularly limited, and such as, can manufacture by making the interfacial polymerization of dihydric phenol and carbonate precursor direct reaction.

As the industrially preparing process with the PC resin of branched structure utilizing interfacial polymerization, what such as adopt is following method: in the alkaline aqueous solution of dihydric phenol, add organic solvent, be blown into the carbonate precursor such as carbonyl chloride wherein and generate the polycarbonate oligomer with reactive chloroformic acid ester group, while the generation of this polycarbonate oligomer or in turn under the existence of polymerizing catalyst and alkaline aqueous solution, further condensation reaction (polyreaction) is carried out to polycarbonate oligomer and branching agent, dihydric phenol and end-capping reagent.It should be noted that, the manufacture method of PC resin of the present invention is not limited to above-mentioned interfacial polymerization.

(branching agent)

In the present invention, under the state keeping good mobility in high shear force areas, improve melting tension force as mentioned above, preferably use 4 officials can above branching agent.

Can above branching agent as 4 officials, such as, penta hydroxy group biphenyl can be enumerated, Pyromellitic Acid, 1,1,2,2-tetra-(4-hydroxy phenyl) ethane, α, α, α ', α '-four (4-hydroxy phenyl)-p-Xylol, α, α, α ', α '-four (2-methyl-4-hydroxy phenyl)-p-Xylol, α, α, α ', α '-four (2,5-dimethyl-4-hydroxy phenyl)-p-Xylol, α, α, α ', α '-four (2,6-dimethyl-4-hydroxy phenyl)-p-Xylol, α, α '-dimethyl-α, α, α ', α '-four (4-hydroxy phenyl)-p-Xylol, α, α '-dimethyl-α, α, α ', α '-four (3-methyl-4-hydroxy phenyl) m-xylene, two [4,4-bis(4-hydroxyphenyl) cyclohexane], two [two (the 4-hydroxy-3-methyl phenyl) hexanaphthene of 4,4-], two [two (3, the 5-dimethyl-4-hydroxy phenyl) hexanaphthene of 4,4-], two [two (4-hydroxy phenyl) cyclohexyl of 4,4-] methane, two [two (the 4-hydroxy-3-methyl phenyl) cyclohexyl of 4,4-] methane, two [two (3, the 5-dimethyl-4-hydroxy phenyl) cyclohexyl of 4,4-] methane, 1,1-two [two (4-hydroxy phenyl) cyclohexyl of 4,4-] ethane, 1,1-two [two (the 4-hydroxy-3-methyl phenyl) cyclohexyl of 4,4-] ethane, 1,1-two [two (3, the 5-dimethyl-4-hydroxy phenyl) cyclohexyl of 4,4-] ethane, 2,2-two [two (4-hydroxy phenyl) cyclohexyl of 4,4-] propane, 2,2-two [two (the 4-hydroxy-3-methyl phenyl) cyclohexyl of 4,4-] propane, 2,2-two [two (3, the 5-dimethyl-4-hydroxy phenyl) cyclohexyl of 4,4-] propane, 2,2-two [two (4-hydroxy phenyl) cyclohexyl of 4,4-] butane, 2,2-two [two (the 4-hydroxy-3-methyl phenyl) cyclohexyl of 4,4-] butane, 2,2-two [two (3, the 5-dimethyl-4-hydroxy phenyl) cyclohexyl of 4,4-] butane, 1,1-two [two (4-hydroxy phenyl) cyclohexyl of 4,4-] hexanaphthene, 1,1-two [two (the 4-hydroxy-3-methyl phenyl) cyclohexyl of 4,4-] hexanaphthene, 1,1-two [two (3, the 5-dimethyl-4-hydroxy phenyl) cyclohexyl of 4,4-] hexanaphthene, 1,1-two [two (4-hydroxy phenyl) cyclohexyl of 4,4-]-1-diphenylphosphino ethane, 1,1-two [two (the 4-hydroxy-3-methyl phenyl) cyclohexyl of 4,4-]-1-diphenylphosphino ethane, 1,1-two [two (3, the 5-dimethyl-4-hydroxy phenyl) cyclohexyl of 4,4-]-1-diphenylphosphino ethane, BP-2, 2,3,4,4'-Tetrahydroxybenzophenone, two (2, the 4-dihydroxy phenyl) propane of 2,2-, two (3,5-dihydroxy phenyl) propane of 2,2-etc.

In addition, the compound that following chemical formula (A) can be used to represent can above branching agent as 4 officials.

[changing 1]

In above-mentioned formula (A), R ¹and R ²represent carbonatoms be 1 ~ 8 alkyl or carbonatoms be the aryl of 6 ~ 20.N is the integer of 1 ~ 100, is preferably the integer of 1 ~ 50.As abovementioned alkyl, such as, methyl, ethyl, propyl group, butyl etc. can be enumerated, as above-mentioned aryl, such as, can phenyl etc. be enumerated.R ¹and R ²respective independence, identical or different.In the compound that above-mentioned formula (A) represents, preferred R ¹and R ²for four (4-hydroxy phenyl-polymethyl siloxane) silicon of methyl.

Above-mentioned 4 officials can be used alone a kind by branching agent above, also can share two or more.

Above-mentioned 4 officials in branching agent above, preferably can use 1,1,2,2-tetra-(4-hydroxy phenyl) ethane, 2,2-two [4, two (4-hydroxy phenyl) cyclohexyl of 4-] propane, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,2-two (2,4-dihydroxy phenyl) compound that represents of propane, 2,2-two (3,5-dihydroxy phenyl) propane and above-mentioned chemical formula (A).

In addition, in the scope not destroying effect of the present invention, can share 3 officials can following branching agent.Can following branching agent as 3 officials, such as, 1 can be enumerated, 1,1-tri-(4-hydroxy phenyl) ethane, α, α ', α "-three (4-hydroxy phenyls)-1,3; 5-triisopropylbenzene, 1-[Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl]-4-[α '; α '-bis-(4 "-hydroxy phenyl) ethyl] benzene, Phloroglucinol, isatin di-(ortho-cresol) etc., these can be used alone a kind, also can share two or more.

(dihydric phenol)

As dihydric phenol, such as, can 1 be enumerated, two (4-hydroxy phenyl) methane of 1-, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane of 2-, two { (4-hydroxyl-3, 5-dimethyl) phenyl } methane, 2, two { (4-hydroxy-3-methyl) phenyl } propane of 2-, 2, two { (the 4-hydroxyl-3 of 2-, 5-dimethyl) phenyl } propane, 2, two { (3-sec.-propyl-4-hydroxyl) phenyl } propane of 2-, 2, two { (4-hydroxyl-3-phenyl) phenyl } propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-the hydroxy phenyl)-3-methylbutane of 2-, 2, two (the 4-hydroxy phenyl)-3 of 2-, 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-2-methylbutane of 4-, 2, two (4-hydroxy phenyl) pentane of 2-, 2, two (4-hydroxy phenyl) paraffinic hydrocarbonss such as two (4-the hydroxy phenyl)-4-methylpentanes of 2-, two (4-hydroxy phenyl) naphthenic hydrocarbon such as 1,1-bis(4-hydroxyphenyl) cyclohexane, 1,1-two (4-hydroxy phenyl)-4-normenthane, 1,1-two (4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexanes, quinhydrones, Resorcinol, 4, 4 '-dihydroxybiphenyl, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane of 1-, 9, two (4-hydroxy phenyl) fluorenes of 9-, 9, two { (4-hydroxy-3-methyl) phenyl } fluorenes of 9-, α, α '-bis-(4-hydroxy phenyl) adjacent diisopropyl benzene, α, diisopropyl benzene between α '-bis-(4-hydroxy phenyl), α, α '-bis-(4-hydroxy phenyl) is to diisopropyl benzene, 1, two (the 4-hydroxy phenyl)-5 of 3-, 7-dimethyladamantane, two (4-hydroxy phenyl) oxide compound, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) ketone, 4, 4 '-dihydroxybiphenyl ether and 4, 4 '-dihydroxybiphenyl ester etc.

In above-mentioned dihydric phenol, preferred use 2, two (4-hydroxy phenyl) propane of 2-, 2, two { (4-hydroxy-3-methyl) phenyl } propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-the hydroxy phenyl)-3-methylbutane of 2-, 2, two (the 4-hydroxy phenyl)-3 of 2-, 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-4-methylpentane of 2-, 1, two (the 4-hydroxy phenyl)-3 of 1-, 3, 5-trimethyl-cyclohexane, α, diisopropyl benzene between α '-bis-(4-hydroxy phenyl), particularly preferably use 2, two (4-hydroxy phenyl) propane [common name dihydroxyphenyl propane] of 2-.In addition, as dihydric phenol, the homopolymer of a kind of above-mentioned dihydric phenol can be the use of, also can be the use of multipolymer of more than two kinds.

(carbonate precursor)

As carbonate precursor, be carbonylic halide, carbonyl ester or haloformate etc., two haloformates, diphenyl carbonate, methylcarbonate, diethyl carbonate etc. of carbonyl chloride, dihydric phenol can be enumerated specifically.Above-mentioned carbonate precursor can be used alone a kind, also can share two or more.

(end-capping reagent)

As end-capping reagent, such as, can enumerate phenol, ortho-cresol, meta-cresol, p-cresol, p-tert-butylphenol, to tert-octyl phenol, p-cumylphenol, nonylphenol, bromo phenol, tribromophenol, docosyl phenol, tetracosyl phenol, ceryl phenol, octacosyl phenol, triacontyl phenol, dotriacontyl phenol, tetratriacontane base phenol etc.In addition, following chemical formula (B) can be used, the monohydric phenol of polyterpene that (C) represents [in formula (B) and (C), p represents the integer of 0 ~ 4] is as end-capping reagent.Above-mentioned end-capping reagent can be used alone a kind, also can share two or more.

In above-mentioned end-capping reagent, preferably use p-tert-butylphenol, p-cumylphenol.

[changing 2]

(catalyzer)

Be suitable as catalyzer phase-transfer catalyst, such as, can preferably use tertiary amine or its salt, quaternary ammonium salt, quaternary alkylphosphonium salt etc.

As tertiary amine, such as, triethylamine, Tributylamine, N, N-dimethylcyclohexylamine, pyridine, xylidine etc. can be enumerated, in addition, as tertiary ammonium salt, such as, can enumerate the hydrochloride of these tertiary amines, bromate etc.As quaternary ammonium salt, such as can enumerate trimethyl benzyl ammonia chloride, triethyl benzyl ammonia chloride, tributyl benzyl ammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide etc., as quaternary alkylphosphonium salt, such as, can enumerate tetrabutylphosphonium chloride, tetrabutyl phosphonium bromide phosphine etc.Above-mentioned catalyzer can be used alone a kind, also can share two or more.

In above-mentioned catalyzer, preferred tertiary amine, especially triethylamine is suitable.

(organic solvent)

As organic solvent, inert organic solvents is suitable, such as, can preferably use chlorinated hydrocarbon, toluene, methyl phenyl ketone etc.

As chlorinated hydrocarbon, such as, methylene dichloride (methylene dichloride), trichloromethane, tetracol phenixin, 1 can be enumerated, 1-ethylene dichloride, 1,2-ethylene dichloride, 1,1,1-trichloroethane, vinyl trichloride, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentaline, chlorobenzene etc.Above-mentioned organic solvent can be used alone a kind, also can share two or more.In above-mentioned organic solvent, especially methylene dichloride is suitable.

(alkaline aqueous solution)

As alkaline aqueous solution, use the alkaline aqueous solution that alkali source is alkali metal hydroxide.As alkali-metal oxyhydroxide, such as, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide etc. can be enumerated.In above-mentioned alkali-metal oxyhydroxide, sodium hydroxide and potassium hydroxide are suitable.

[poly carbonate resin composition]

In addition, the invention provides the poly carbonate resin composition of polycarbonate resin containing above-mentioned and additive.

As above-mentioned additive, even also guarantee excellent flame retardant resistance in order to products formed that thickness is thinner, preferably use fire retardant.

(fire retardant)

As fire retardant, such as, the organic metal salt such as organic alkali metal salt, organic bases earth metal salt flame retardant, silicone flame retardant, phosphorus flame retardant, phosphonitrile flame retardant etc. can be used, wherein preferably use organic alkali metal salt and such organic metal salt flame retardant, silicone flame retardant and the phosphorus flame retardant of organic bases earth metal salt.Fire retardant can be used alone a kind, also can share two or more.

The content of fire retardant is preferably 0.005 ~ 12 mass parts relative to polycarbonate resin 100 mass parts, is more preferably 0.01 ~ 10 mass parts, more preferably 0.15 ~ 9 mass parts.If the content of fire retardant is more than 0.005 mass parts, sufficient flame retardant resistance can be obtained, if then sufficient mechanical property can be obtained below 12 mass parts.

< organic metal salt flame retardant >

Above-mentioned organic metal salt flame retardant is preferably organic alkali metal salt and organic bases earth metal salt.

Various material can be enumerated as organic alkali metal salt and organic bases earth metal salt, can use and there is the organic acid of at least one carbon atom or an alkali metal salt of organic acid acetic and organic bases earth metal salt.

Herein, organic acid or organic acid acetic are such as organic sulfonic acid, organic carboxyl acid etc.In addition, basic metal is lithium, sodium, potassium, caesium etc., and alkaline-earth metal is magnesium, calcium, strontium, barium etc., wherein, preferably uses the salt of sodium, potassium.In addition, this organic acid salt can replace the halogen having fluorine, chlorine, bromine and so on.Organic alkali metal salt and organic bases earth metal salt can be used alone a kind, also can share two or more.

In above-mentioned various organic alkali metal salt and organic bases earth metal salt, such as, when organic sulfonic acid, an alkali metal salt of the perfluoroalkane hydrocarbon sulfonate preferably using following general formula (I) to represent and alkaline earth salt.

(C _eF _2e+1SO ₃) _fM (I)

In formula, e represents the integer of 1 ~ 10, and M represents the alkaline-earth metal such as the basic metal such as lithium, sodium, potassium, caesium, magnesium, calcium, strontium, barium, and f represents the valence of M.

As these compounds, such as, the compound recorded in Japanese Patent Publication 47-40445 publication is equivalent to this.

In above-mentioned general formula (I), as perfluoroalkane hydrocarbon sulfonate, such as, perfluor methylsulfonic acid, perfluor ethyl sulfonic acid, perfluor propanesulfonic acid, perfluor fourth sulfonic acid, perfluoro-methyl fourth sulfonic acid, the own sulfonic acid of perfluor, perfluor sulfonic acid in heptan, perfluorooctane sulfonate etc. can be enumerated.Especially their sylvite is preferably used.

As an alkali metal salt and the alkaline earth salt of the organic sulfonic acid beyond above-mentioned general formula (I), such as, can 2 be enumerated, 5-dichloro benzosulfonic acid, 2,4, the an alkali metal salt of the organic sulfonic acids such as 5-trichlorobenzene sulfonic acid, sulfobenzide-3-sulfonic acid, sulfobenzide-3,3 '-disulfonic acid, naphthalene trisulfonic acid and alkaline earth salt etc.

In addition, as organic carboxyl acid, such as, perfluor formic acid, perfluoromethane carboxylic acid, R 116 carboxylic acid, perfluoropropane carboxylic acid, perfluorinated butane carboxylic acid, perfluoro-methyl butane carboxylic acid, perflexane carboxylic acid, PF 5070 carboxylic acid, PFO carboxylic acid etc. can be enumerated, an alkali metal salt and the alkaline earth salt of these organic carboxyl acids can be used.

Then, as organic alkali metal salt and organic bases earth metal salt, an alkali metal salt and the alkaline earth salt of polystyrolsulfon acid can be enumerated, such as, the aromatic vinyl base system resin containing sulphonate-base that following general formula (II) can be used to represent.

[changing 3]

In above-mentioned formula (II), Z ¹represent sulphonate-base, Z ²represent that hydrogen atom or carbonatoms are the alkyl of 1 ~ 10.G is the integer of 1 ~ 5.H represents molar fraction, 0 < h≤1.

Herein, sulphonate-base is an alkali metal salt and/or the alkaline earth salt of sulfonic acid, as metal, can enumerate sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium etc.

In formula, Z ²to be hydrogen atom or carbonatoms be 1 ~ 10 alkyl, be preferably hydrogen atom or methyl.In addition, g is the integer of 1 ~ 5, and h meets the relation of 0 < h≤1.That is, for aromatic ring, sulphonate-base (Z ¹) can all replace, also can partly replace.

In order to improve the flame resistance effect of poly carbonate resin composition of the present invention further, the replacement ratio of sulphonate-base considers that the content etc. of the aromatic vinyl base system resin containing sulphonate-base decides, the aromatic vinyl base system resin generally speaking using 10 ~ 100% to replace.

It should be noted that, in an alkali metal salt of polystyrolsulfon acid and alkaline earth salt, aromatic vinyl base system resin containing sulphonate-base is not limited to the polystyrene resin of above-mentioned general formula (II), also can be styrenic monomers with can the multipolymer of other monomer of copolymerization.

Herein, as containing the manufacture method of sulphonate-base aromatic vinyl base system resin, by the following method: (1) by the above-mentioned aromatic vinyl base system monomer with sulfonic group etc. or by they with can other monomer polymerization of copolymerization or the method for copolymerization; (2) can the multipolymer of monomer of copolymerization or these mixed polymer sulfonation by aromatic ethenyl based polymer or aromatic vinyl base system monomer and other, the method etc. neutralized is carried out with alkali metal compound and/or alkaline earth metal compound.

Such as, as the method for above-mentioned (2), heated by the mixed solution adding the vitriol oil and diacetyl oxide in 1,2-dichloroethane solution of polystyrene resin, stoichiometric number hour, manufactures polystyrolsulfon acid compound.Then, by with in the potassium hydroxide of equimolar amount or sodium hydroxide and sulfonic group can obtain polystyrolsulfon acid sylvite or sodium salt.

As the weight-average molecular weight containing sulphonate-base aromatic vinyl base system resin used in the present invention, be 1,000 ~ 300, about 000, be preferably 2,000 ~ 200, about 000.It should be noted that, weight-average molecular weight can utilize GPC method to measure.

< silicone flame retardant >

As above-mentioned silicone flame retardant, such as, can organic silicone oil, silicone resin etc. be enumerated, the silicoorganic compound etc. with functional group can also be enumerated.

As the silicoorganic compound with above-mentioned functional group, there is various compound, such as, (gathering) the organo-siloxane class with functional group can be enumerated, as its skeleton, be polymkeric substance, the multipolymer with the foundation structure that following general formula (III) represents.

R ³ _aR ⁴ _bSiO _(4-a-b)/2(III)

In above-mentioned formula (III), R ³represent group, the R containing functional group ⁴represent that carbonatoms is the alkyl of 1 ~ 12,0 < a≤3,0≤b < 3,0 < a+b≤3.

In addition, as functional group, alkoxyl group, aryloxy, polyoxy alkylidene, hydrogen atom, hydroxyl, carboxyl, silanol base, amino, sulfydryl, epoxy group(ing) etc. can be enumerated.

As these functional groups, the silicoorganic compound with multiple functional group, the silicoorganic compound with different functional groups can also be share.The silicoorganic compound with this functional group are its functional group (R ³)/alkyl (R ⁴) be generally 0.1 ~ 3, be preferably the compound of about 0.3 ~ 2.These silicoorganic compound are liquid object, powder etc., but the material of preferred favorable dispersity in melting mixing.Such as, the viscosity that can illustrate under room temperature is the material of the liquid state of 10 ~ 500,000cst (centistoke) left and right.When silicoorganic compound have functional group, even if silicoorganic compound are liquid, there is following feature, disperse equably in the composition, and the situation escaping to the surface of products formed time shaping are few.

< phosphorus flame retardant >

As above-mentioned phosphorus flame retardant, preferably not halogen-containing phosphorus flame retardant.If halogen-containing, then the risk of the generation of obnoxious flavour when existing shaping, mould corrosion, and the risk of discharging objectionable impurities during the incineration of products formed, not preferred from the viewpoint of environmental pollution, security.

As not halogen-containing phosphorus flame retardant, there is the organic phosphorus flame retardant not containing halogen.As organic phosphorus flame retardant, if there is phosphorus atom and not halogen-containing organic compound then can use ad lib.Wherein, the phosphate compound of the ester Sauerstoffatom with more than 1 and phosphorus atom Direct Bonding is preferably used.As the phosphorus flame retardant not containing halogen beyond organophosphorus based compound, there is red phosphorus etc.

As phosphate compound, be not particularly limited, the phosphate compound such as represented for following general formula (IV).

[changing 4]

In formula, R ⁵, R ⁶, R ⁷and R ⁸represent hydrogen atom or organic group independently of one another, X represents the organic group of more than divalent, s be 0 or 1, t be the integer of more than 1, r represents the integer of more than 0.

In above-mentioned formula (IV), organic group is the alkyl, cycloalkyl, aryl etc. that can be substituted, also can not be substituted.In addition, as substituting group when being substituted, there are alkyl, alkoxyl group, aryl, aryloxy, arylthio etc.Also have the organic group etc. as the alternatively base such as the alkoxy aryl alkyl etc. being combined with these substituent groups or the aryl sulfonyl aryl that is combined into by these substituting groups of the bondings such as Sauerstoffatom, nitrogen-atoms, sulphur atom.

In addition, in formula (IV), as organic group X more than divalent, refer to that removing is bonded to the group of more than the divalent of more than 1 of the hydrogen atom of carbon atom from above-mentioned organic group.Be such as alkylidene group, (replacement) phenylene, by the derivative group of the bisphenols as multinuclear phenols.As preferably, dihydroxyphenyl propane, Resorcinol, Resorcinol, ditan, dihydroxybiphenyl and dihydroxy naphthlene etc. can be enumerated.

Phosphate compound can be monomer, dimer, oligopolymer, polymer or their mixture.Specifically, trimethyl phosphite 99 can be enumerated, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate (butoxyethyl group) ester, triphenylphosphate, Tritolyl Phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri-2-ethylhexyl phosphate, diisopropyl phenyl phosphoric acid ester, trixylyl phosphate, tricresyl phosphate isopropyl phenyl ester, tri naphthyl phosphate, dihydroxyphenyl propane biphosphonate, Resorcinol biphosphonate, Resorcinol biphosphonate, Resorcinol-diphenyl phosphoester, benzenetriol triguaiacyl phosphate, phosphate toluene diphenyl ester, or their substituent, condenses etc.

(additive beyond fire retardant)

In poly carbonate resin composition of the present invention, as the additive beyond above-mentioned fire retardant, inorganic filling material can be used; The antioxidants such as hindered phenol system, phosphorous acid ester system and phosphoric acid ester system; The photostabilizer such as UV light absorber, hindered amine system of benzotriazole system, benzophenone series etc.; The exterior lubricant such as aliphatic carboxylic acid esters, system, alkane hydrocarbon system; Tinting material, flame retardant, static inhibitor etc.

As above-mentioned inorganic filling material, various material can be used, specifically, glass material, carbon fiber, other inorganic filling material can be used.

First, as glass material, such as, glass fibre, glass microballon, glass flake, glass powder etc. can be used.Herein, as used glass fibre, can be any one in alkali-containing glass, glass with lower alkali content, non-alkali glass.Its fiber length is about 0.1 ~ 8mm, and be preferably 0.3 ~ 6mm, in addition, fiber footpath is about 0.1 ~ 30 μm, is preferably 0.5 ~ 25 μm.Further, the form of this glass fibre is not particularly limited, and such as, can enumerate the various forms such as rove, milled fiber (milled fiber), chopped strand (chopped strand).These glass fibre can be used alone a kind, also can share two or more.

In addition, in order to improve the affinity with resin, glass material can be carry out the glass material after surface treatment with silane series coupling agent, chromium complex or boron compounds etc. such as amino silicone methane series, epoxy silane system, vinyl silanes system, methacryl silanes systems.As such glass material, such as, Asahi Fiber Glass Co. can be used aptly as commercially available material, the MA-409C (13 μm, average fiber footpath) of Ltd or TA-409C (23 μm, average fiber footpath) etc.

Then, as carbon fiber, generally using cellulosic fibre, acrylic fibers, xylogen, oil or carbobitumen etc. as raw material, manufacturing by firing, having various types of carbon fibers such as resistance to flame matter, carbonaceous or graphite.The fiber length of carbon fiber is about 0.01 ~ 10mm, and preferably in the scope of 0.02 ~ 8mm, in addition, fiber footpath is about 1 ~ 15 μm, is preferably 5 ~ 13 μm.Further, the form of this carbon fiber is not particularly limited, and such as, can enumerate the various forms such as rove, milled fiber, chopped strand, precursor (strand).These carbon fibers can be used alone a kind, also can share two or more.

In addition, in order to improve the affinity with resin, the surface of these carbon fibers can be implemented surface-treated surface with epoxy resin, carbamate resins etc.As such carbon fiber, such as, Toho Rayon Co. can be used aptly as commercially available carbon fiber, the Besfite (7 μm, average fiber footpath) etc. of Ltd.

As other inorganic filling material, such as, aluminum fiber, calcium carbonate, magnesiumcarbonate, rhombspar, silicon-dioxide, diatomite, aluminum oxide, titanium dioxide, ferric oxide, zinc oxide, magnesium oxide, calcium sulfate, magnesium sulfate, calcium sulfite, talcum, clay, mica, asbestos, Calucium Silicate powder, montmorillonite, wilkinite, carbon black, graphite, iron powder, lead powder, aluminium powder etc. can be used.

Poly carbonate resin composition can by utilizing normally used method, such as using the method for ribbon blender (ribbon blender), Henschel mixer (trade(brand)name), Banbury, drum tumbler (drumtumbler), single screw extrusion machine, twin screw extruder, kneading extruder, multiple screw extruder etc. to carry out mixture aforesaid PC resin and various additive carries out mixing and obtains.Heating temperature time mixing is selected usually in the scope of 250 ~ 300 DEG C.

[products formed]

In addition, the invention provides aforesaid polycarbonate resin or the shaping products formed of aforesaid poly carbonate resin composition.Especially from keeping shaping mobility and the characteristic of the PC resin of the raising of melting tension force, anti-dropping excellence, as the method for forming, blow molding is suitable, the invention provides the products formed of blow molding.

Polycarbonate resin or poly carbonate resin composition can apply the known various methods of forming except above-mentioned blow molding, such as, and injection moulding, extrusion moulding, compressed moulding, calendering formation, rotoforming etc.By these methods of forming, can Production Example as, the products formed of the various industrial use such as illuminating cover, indicating meter protective guard, OA equipment, electric and electronic field.

For polycarbonate resin of the present invention, from maintenance shaping mobility and melting tension force improve, anti-dropping excellence, this polycarbonate resin and the poly carbonate resin composition comprising it have anti-dropping and do not need to cause the additives such as opaque PTFE.Therefore, the polycarbonate resin of the application of the invention and the poly carbonate resin composition that comprises it can provide the products formed of the transparency and excellent in flame retardance.

Embodiment

By following embodiment, illustrate the present invention further, but the present invention does not limit by these embodiments.

[physical property measurement method]

(primary structure)

Viscosity-average molecular weight: Mv

Use Ubbelohde viscometer, the viscosity of dichloromethane solution when measuring 20 DEG C, obtains limiting viscosity [η], thus by [η]=1.23 × 10 ^-5mv ^0.83calculate viscosity-average molecular weight (Mv).

Branching agent content

Jeol Ltd.'s system, JNM-LA500 are used for obtained thin slice, measures ¹h-NMR, calculates the branching agent content (mol%) of the branching agent of use by formula below.

Branching agent content (mol%)=[coming from the structural unit (mol) of branching agent/[coming from the structural unit (mol) of the structural unit (mol) of the structural unit (mol) of dihydric phenol+come from end-capping reagent+come from branching agent]] × 100

(melting characteristic)

Melt fluidity: MVR

Use peace Tian Jingji Co., Ltd. system, implementor name MFR meter E machine, with 280 DEG C, load 2.16kg mensuration melt fluidity MVR (cm ³/ 10 minutes).

Melting tension force: MT

Use Toyo Co., Ltd.'s essence mechanism to make made, implementor name Capirograph 1C, with 280 DEG C, hole (orifice) footpath L/D=8/2.095mm, extruded velocity 10mm/ minute, pulling speed 3.1m/ minute measure melting tension force MT (g).

Embodiment 1

(1) polycarbonate oligomer synthesis procedure (linear oligomer)

Adding relative to the dihydroxyphenyl propane dissolved afterwards (below sometimes referred to as BPA) in 5.6 quality % aqueous sodium hydroxide solutions is 2, the V-Brite B of 000 quality ppm, dissolve dihydroxyphenyl propane wherein and become 13.5 quality % to make bisphenol A concentration, prepare the aqueous sodium hydroxide solution of dihydroxyphenyl propane.

By the aqueous sodium hydroxide solution 40L/ of dihydroxyphenyl propane hour and methylene dichloride 15L/ hour and the tube-type reactor passing into internal diameter 6mm, pipe range 30m for carbonyl chloride 4.0kg/ hour continuously.Tube-type reactor has chuck (jacket) part, passes into water coolant the temperature of reaction solution is remained on less than 40 DEG C in chuck.

Flow out the reaction solution of tube-type reactor to import continuously in the tank reactor of the band baffle plate of the internal volume 40L possessing scraping blade (sweptback wing), add further wherein aqueous sodium hydroxide solution 2.8L/ hour of dihydroxyphenyl propane, 25 quality % aqueous sodium hydroxide solution 0.07L/ hour, water 17L/ hour and 1 quality % triethylamine aqueous solution react for 0.64L/ hour.

The reaction solution overflowed from tank reactor is extracted out continuously, by leaving standstill, aqueous phase separation being removed, gathering methylene dichloride phase.The concentration of the polycarbonate oligomer obtained is 324g/L, chloroformic acid ester group concentration is 0.74mol/L.

(2) polymerization process of polycarbonate

In the 1L tank reactor possessing balk board, paddle stirring rake, drop into oligomer solution 340mL, methylene dichloride 180mL, triethylamine 70 μ L.

Add the aqueous sodium hydroxide solution (by the aqueous solution of water-soluble for sodium hydroxide 2.35g 34mL, dissolving THBP1.30g) of branching agent BP-2 (THBP) wherein, implement 10 minutes polyreactions.

Next, be added on the aqueous sodium hydroxide solution (solution by after making V-Brite B 50mg, BRA25.2g dissolve after in water-soluble for sodium hydroxide 13.1g 190mL) that methylene dichloride 30mL dissolves the solution after p-tert-butylphenol (PTBP) 4.92g and BPA and implement 50 minutes polyreactions.

After adding methylene dichloride 200mL to carry out diluting, being separated into the organic phase comprising polycarbonate resin and the aqueous phase of the BPA and sodium hydroxide comprising surplus, isolating organic phase.For the dichloromethane solution of obtained polycarbonate resin, successively with the 0.03mol/L aqueous sodium hydroxide solution and the 0.2mol/L hydrochloric acid cleaning that relative to this solution are 15 capacity %, then repeatedly clean with pure water until the specific conductivity of aqueous phase after cleaning becomes 0.05 below μ S/m.Dichloromethane solution by cleaning the polycarbonate resin obtained is concentrated, pulverizing, under reduced pressure carries out drying in 100 DEG C by obtained thin slice, obtains polycarbonate resin.

For obtained polycarbonate resin, the viscosity-average molecular weight after the method for carrying out above, branching agent content, melting tension force, melt fluidity are shown in table 1.In addition, relation (MT) × (1/MVR) of melting tension force shown in Figure 1 and melt fluidity.

Comparative example 1

(1) polycarbonate oligomer synthesis procedure (branched oligomer)

In 5.6 quality % aqueous sodium hydroxide solutions, 2 are added relative to the dihydroxyphenyl propane (below sometimes referred to as BPA) in rear dissolving, the V-Brite B of 000 quality ppm, dissolving dihydroxyphenyl propane wherein becomes 13.5 quality % to make bisphenol A concentration, prepares the aqueous sodium hydroxide solution of dihydroxyphenyl propane.In addition, in 5.1 quality % aqueous sodium hydroxide solutions, add the branching agent 1 relative to dissolving afterwards, 1,1-tri-(4-hydroxy phenyl) ethane (THPE) is 4, the V-Brite B of 000 quality ppm, dissolves in the mode making THPE concentration become 11.3 quality % wherein, the aqueous sodium hydroxide solution of preparation THPE.

By aqueous sodium hydroxide solution 1.4L/ hour of the aqueous sodium hydroxide solution 40L/ of dihydroxyphenyl propane hour and THPE, methylene dichloride 15L/ hour and passing into continuously in the tube-type reactor of internal diameter 6mm, pipe range 30m for carbonyl chloride 4.0kg/ hour.Tube-type reactor has jacket portion, passes into water coolant the temperature of reaction solution is remained on less than 40 DEG C in chuck.

Flow out the reaction solution of tube-type reactor to import continuously in the tank reactor of the band traverse baffle of the internal volume 40L possessing scraping blade (sweptback wing), add further wherein aqueous sodium hydroxide solution 2.8L/ hour of dihydroxyphenyl propane, 25 quality % aqueous sodium hydroxide solution 0.07L/ hour, water 17L/ hour and 1 quality % triethylamine aqueous solution react for 0.64L/ hour.

The reaction solution overflowed from tank reactor is extracted out continuously, by leaving standstill, aqueous phase separation being removed, gathering methylene dichloride phase.The concentration of the polycarbonate oligomer obtained is 354g/L, and chloroformic acid ester group concentration is 0.70mol/L.

(2) polymerization process of polycarbonate

In the 1L tank reactor possessing balk board, paddle stirring rake, drop into oligomer solution 310mL, methylene dichloride 210mL, p-tert-butylphenol (PTBP) 3.66g, triethylamine 60 μ L.

At this, the aqueous sodium hydroxide solution (by water-soluble for sodium hydroxide 11.3g 165mL, making the solution that V-Brite B 50mg, BPA21.8g dissolve) adding BPA implements 60 minutes polyreactions.

In order to carry out after dilution adds methylene dichloride 200mL, be separated into the organic phase that comprises polycarbonate resin and comprising superfluous BPA and the aqueous phase of sodium hydroxide, isolating organic phase.For the dichloromethane solution of obtained polycarbonate resin, successively with the 0.03mol/L NaOH aqueous solution and the 0.2mol/L hydrochloric acid cleaning that relative to this solution are 15 capacity %, then repeatedly clean with pure water until the specific conductivity in aqueous phase after cleaning becomes 0.05 below μ S/m.Dichloromethane solution by cleaning the polycarbonate resin obtained is concentrated, pulverizing, under reduced pressure carries out drying in 100 DEG C by obtained thin slice, obtains polycarbonate resin.

For obtained polycarbonate resin, the viscosity-average molecular weight of being undertaken by above-mentioned method, branching agent content, melting tension force, melt fluidity are shown in table 1.In addition, relation (MT) × (1/MVR) of melting tension force shown in Figure 1 and melt fluidity.It should be noted that, because THPE is dropped into continuously by circulation reaction system, therefore in table 1, branching dosage [g] represents with "-".

Embodiment 2 ~ 15 and comparative example 3 ~ 10

Branching agent kind, branching dosage, PTBP amount in embodiment 1 are changed according to table 1 respectively, implements similarly to Example 1 in addition.

For obtained polycarbonate resin, the viscosity-average molecular weight of being undertaken by above-mentioned method, branching agent content, melting tension force, melt fluidity are shown in table 1.In addition, relation (MT) × (1/MVR) of melting tension force shown in Figure 1 and melt fluidity.

Comparative example 2

In comparative example 1, except change PTBP amount according to table 1 except, implement in the same manner as comparative example 1.

[table 1]

Table 1

THBP (4 officials' energy): BP-2

TEPDF (4 officials' energy): 1,1,2,2-tetra-(4-hydroxyphenyl) ethane

BOCP (4 officials' energy): 2,2-two [two (4-hydroxyphenyl) cyclohexyl of 4,4-] propane

THPE (3 officials' energy): 1,1,1-tri-(4-hydroxyphenyl) ethane

Industry utilizes possibility

Because polycarbonate resin of the present invention can keep shaping mobility; and melting tension force improves, anti-dropping is excellent; therefore this polycarbonate resin and the poly carbonate resin composition that comprises it can provide the products formed of the transparency and excellent in flame retardance; such as, be suitable in the various industrial uses such as illuminating cover, indicating meter protective guard, OA equipment, electric and electronic field.

Nomenclature

The straight line of 1 MT=(15.4/MVR)-1.3

The straight line of 2 MT=(57.14/MVR)-1.3

The straight line of 3 MT=(20.6/MVR)-2.1

Claims

1. a polycarbonate resin, the melting tension force MT [g] when its 280 DEG C and melt fluidity MVR [cm when 280 DEG C ³/ 10 minutes] relation meet formula (1) ~ (3) below,

Formula (1): MT >=(15.4/MVR)-1.3

Formula (2): MT≤(57.4/MVR)-1.3

Formula (3): MT >=1

2. polycarbonate resin according to claim 1, it comprises the polycarbonate resin with branched structure.

3. polycarbonate resin according to claim 1, it comprises and has the polycarbonate resin of branched structure and the polycarbonate resin of straight-chain.

5. a poly carbonate resin composition, it contains polycarbonate resin according to any one of Claims 1 to 4 and additive.

6. poly carbonate resin composition according to claim 5, wherein, described additive is fire retardant.

7. a products formed, its be by the polycarbonate resin according to any one of Claims 1 to 4 or the poly carbonate resin composition described in claim 5 or 6 shaping.

8. products formed according to claim 7, it is that blow molding forms.