WO2007114060A1

WO2007114060A1 - Polycarbonate-hydrogenated polybutadiene copolymer, method for producing same, and polycarbonate resin composition using same

Info

Publication number: WO2007114060A1
Application number: PCT/JP2007/055830
Authority: WO
Inventors: Masaya Okamoto
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2006-03-31
Filing date: 2007-03-22
Publication date: 2007-10-11
Also published as: TW200808869A

Abstract

Disclosed is a polycarbonate-hydrogenated polybutadiene copolymer containing repeating units (I) and (II) having specific structures. Also disclosed is a polycarbonate resin composition obtained by melt-mixing a blend which is obtained by blending the polycarbonate-hydrogenated polybutadiene copolymer (iii) into a mixture of 45-99% by mass of a polycarbonate resin (i) and 55-1% by mass of a polyolefin resin (ii) in an amount of 0.1-30 parts by mass per 100 parts by mass of the resin mixture. The polycarbonate resin composition is improved in compatibility between the polycarbonate resin and the polyolefin resin, while having impact resistance, fluidity and chemical resistance without suffering from lamellar separation.

Description

Specification

Polycarbonate monohydrogenated polybutadiene copolymer, process for producing the same, and polycarbonate resin composition using the same

Technical field

[0001] The present invention relates to a polycarbonate-hydrogenated polybutadiene copolymer and a method for producing the same.

The present invention relates to a polycarbonate resin composition using the same, and particularly to a polycarbonate resin composition excellent in low-temperature impact resistance, fluidity and chemical resistance, which does not exhibit delamination after molding.

Background art

[0002] Polycarbonate resins are engineering plastics excellent in heat resistance, impact resistance, transparency, and the like. It is believed that further properties (low temperature impact resistance, fluidity, chemical resistance) can be imparted by blending polycarbonate resin and polyolefin resin. However, there is a problem that the polycarbonate resin and the polyolefin resin are not compatible with each other, and the mechanical strength is greatly reduced.

[0003] In order to improve the rigidity at high temperature and the impact resistance at low temperature, Patent Document 1 describes that 100 parts by mass of a polypropylene resin is 4, 100 parts by mass of 4,4 dioxydiphenylalkane-based polycarbonate resin. A polypropylene resin composition for improving the rigidity at high temperature, which is formulated by blending, is proposed. However, when this resin composition is used, there is a problem that delamination occurs in the injection-molded product, a streak pattern is generated on the surface, and the appearance is impaired. In addition, Patent Document 2 describes 70 99% by weight of aromatic polycarbonate resin, melt index, density, and maximum peak temperature by differential scanning calorimetry (DSC) measurement method, in order to improve moldability and chemical resistance. And a thermoplastic resin composition containing a boiling n-xane-insoluble content in a predetermined range of ethylene _α -old olefin copolymer:! To 30% by mass, respectively. However, in this case as well, there is a problem that delamination occurs in the injection molded product, streaks appear on the surface, and the appearance is impaired.

[0004] Further, in Patent Document 3 and Patent Document 4, in order to solve the above-mentioned problem of delamination, that is, surface delamination, in order to have a chemical interaction with the polycarbonate resin, it is unsatisfactory. A composition of a Japanese carboxylic acid-modified polyolefin resin and a polycarbonate resin has also been proposed. However, a general polycarbonate resin has a closed end and has no functional group, and thus has no remarkable effect.

[0005] Further, Patent Document 5 discloses a partially or completely crosslinked saturated rubber-like polymer and a polyolefin resin such as a polyolefin resin, a polystyrene resin, a polyamide resin, a polyurethane resin, and a polycarbonate resin. High impact resistance and high functionality thermoplastic resin compositions made of thermoplastic resins other than resins have been proposed. More specifically, (A) a thermoplastic elastomer composed of a partially or completely crosslinked saturated rubber-like polymer and a polyolefin resin: 95 to 5 parts by mass, (B) a thermoplastic resin (polyolefin resin) 5) to 95 parts by mass and (C) compatibilizer: (A) component and (B) component to 100 parts by mass. A high impact thermoplastic resin composition characterized in that a saturated rubber-like polymer in the product is 1 to 40% by mass.

Examples of the polycarbonate-based thermoplastic resin are listed in Example 18. First, using a twin-screw extruder (40πιπι φ, L / D = 47), an ethylene′-octene 1 copolymer ( TPE— 1) / isotactic polypropylene (PP) / radical initiator (POX) / crosslinking aid (DVB) = 6/44. 4/0. 38/0. 74 (mass ratio) A cross-linked thermoplastic elastomer is produced by melt extrusion at a temperature of 220 ° C. In addition to this, acrylonitrile styrene grafted ethylene / propylene / conjugate copolymer, hydrogenated styrene butadiene block copolymer and polycarbonate are melted, kneaded and extruded as pellets with a twin screw extruder. The

In this way, two times of melt extrusion are necessary, and thermal degradation is likely to occur.

Furthermore, recently, a technology for reacting a modified polycarbonate having a functional group with polyolefin in a kneading machine has been reported in academic societies, etc., but a long continuous kneading is required, and a general continuous kneading machine is required. It is not applicable to and is not practical.

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 59-223741

Patent Document 2: JP-A-61-43658

Patent Document 3: JP-A 59-223742

Patent Document 4: Japanese Patent Application Laid-Open No. 59-223749 Patent Document 5: Japanese Patent Laid-Open No. 2001-146533

Disclosure of the invention

[0007] The present invention has been made to solve the above-mentioned problems of the prior art, and improves the compatibility between the polycarbonate resin and the polyolefin resin, and provides impact resistance, fluidity, and chemical resistance. It is an object of the present invention to provide a polycarbonate resin composition having properties such as the above, a polycarbonate polymer suitable as a compatibilizing agent, and a method for producing the same.

As a result of diligent research to achieve the above object, the inventors of the present invention are effective in compatibilizing polycarbonate monohydrogenated polybutadiene copolymer S having a specific structure, polycarbonate resin and polyolefin resin, and reducing the polyolefin domain. Therefore, it has been found that the resin composition obtained by mixing and kneading the copolymer is capable of solving the above-mentioned problems that the layered peeling does not occur at the time of molding.

Further, the present inventors have found that hydrogenated polybutadiene having a phenolic hydroxyl group at the terminal used as a raw material for the polycarbonate monohydrogenated polybutadiene copolymer is a novel compound.

That is, the present invention

(1) A polycarbonate-hydrogenated polybutadiene copolymer having a repeating unit (I) represented by the following general formula (I) and a repeating unit (II) represented by the following general formula (II):

[0008] [Chemical 1]

[Wherein R ¹ and IT are each a halogen atom (for example, chlorine, bromine, fluorine, iodine), an alkoxy group, an ester group, a carboxyl group, a hydroxyl group, or an alkyl group having from 8 to 8 carbon atoms. Alternatively, it may have an alkyl group on a ring having 6 to 20 carbon atoms, and may be an aromatic group, and may be bonded to either the o_ position or the m_ position. If the R ¹ and R ² are a plurality of each, even each R ¹ and R ² are identical to each other or may be different. X is a single bond, a polymethylene group having 1 to 20 carbon atoms, an alkylene group, an alkylidene group, or a cycloalkylene group. Group, s so- so ○ -co—bond or general formula

[Chemical 2]

And a fluorene residue, m and n represent an integer of 0-4. ]

[Chemical 3]

(ID

[In the formula, R ³ is an alkyl group having 1 to 20 carbon atoms, an aryleno group, an aryl alkyl group, Y is a single bond, a polymethylene group having 1 to 10 carbon atoms, an alkylene group, and an alkylidene group, and r is 0. An integer of ~ 4, p is a number of 0 · 00 ~:! · 00, _q is an integer of:! ~ 500. When there are a plurality of R ³ forces S, the plurality of R ³ may be the same or different. ]

(2) Polycarbonate-hydrogenated polybutadiene copolymer according to the above (1), wherein the content power S of the hydrogenated polybutadiene part is S, 0 :! to 50% by mass,

(3) The polycarbonate monohydrogenated polybutadiene copolymer according to the above (1) or (2), having a viscosity average molecular weight of 10,000 to 50,000,

(4) A polycarbonate oligomer is produced by reacting an aromatic dihydroxy compound (A) represented by the following general formula (ΠΙ) with a carbonyl source such as phosgene or diphenyl carbonate, And an aromatic dihydroxy compound (B) represented by the following general formula (IV) and the aromatic dihydroxy compound (A) are mixed in an organic solvent and an alkaline aqueous solution. The method for producing a polycarbonate monohydrogenated polybutadiene copolymer according to any one of (1) to (3), wherein the reaction is carried out under a liquid,

[0012] [Chemical 4]

[Wherein, R ¹ and R ² , m and n, and X are the same as those in the general formula (I). ]

[0014] [Chemical 5]

[In the formula, Y, r, p, and q are the same as in the general formula (Π). When there are multiple R ^{3 s} , the multiple R ^{3 s} may be the same or different from each other. ]

(5) Polycarbonate resin according to any one of the above (1) to (3) per 100 parts by mass in a mixture of polycarbonate resin (i) 45 to 99% by mass and polyolefin resin (55 to 1% by mass) —Hydrogenated polybutadiene copolymer (iii) O .: A polycarbonate resin composition comprising 30 to 30 parts by mass, melt-kneaded,

(6) Polycarbonate resin according to any one of the above (1) to (3) per 100 parts by mass of a mixture of polycarbonate resin (i) 45 to 99% by mass and polyolefin resin (55 to 1% by mass) Hydrogenated polybutadiene copolymer (iii) O .:! ~ 30 parts by mass and compatibilizing aid consisting of styrene-ethylene-butylene-styrene block copolymer (iv) 0.5 ~: 10 parts by mass A polycarbonate resin composition obtained by melt-kneading,

(7) A molded article obtained by melt-molding the polycarbonate resin composition according to (5) or (6), and

(8) a hydrogenated polybutadiene having a phenolic hydroxyl group at the terminal represented by the general formula (IV), Is to provide.

Brief Description of Drawings

FIG. 1 is a perspective view of a test piece mounting jig for evaluating chemical resistance of a resin composition of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] The repeating unit (I) represented by the general formula (I) and the repeating unit represented by the general formula (Π) of the present invention.

A polycarbonate monohydrogenated polybutadiene copolymer having a returning unit (Π) is effective for compatibilization of a polycarbonate resin and a polyolefin resin, and is added to a polycarbonate resin composition containing a polyolefin resin to add a polyolefin domain. Since it can be made small, it is possible to improve low temperature impact resistance and the like that do not cause delamination after molding of the composition.

The effect of the polycarbonate-hydrogenated polybutadiene copolymer as a compatibilizer is that it acts as a surfactant and is present at the interface between the polyolefin resin and the polycarbonate resin to reduce the polyolefin domain.

[0018] Polycarbonate monohydrogenated polybutadiene copolymer

The polycarbonate-hydrogenated polybutadiene copolymer is a polycarbonate-hydrogenated monohydrogenated compound having a repeating unit (I) represented by the following general formula (I) and a repeating unit (Π) represented by the following general formula (II). It is a polybutadiene copolymer.

[0019] [Chemical 6]

In the formula (I), R ¹ and R ² are each a halogen atom (for example, chlorine, bromine, fluorine, iodine), an alkoxy group, an ester group, a carboxyl group, a hydroxyl group, an alkyl group having! It is an aromatic group which may have an alkyl group on the ring having 6 to 20 carbon atoms in total, and may be bonded to either the o-position or the m-position. The R ¹ and R ^2, when Re of the plurality each it, even each R ¹ and R ² are identical to each other or may be different. X is a single bond, a polymethylene group having 1 to 20 carbon atoms, an alkylene group, an alkylidene group, a cycloanolylene group, a cycloanolidene group, S, 1 SO, 1 SO 2—, 1 O—, CO bond Or general formula

[Chemical 7]

And a fluorene residue, m and n represent integers of 0 to 4.

[0021] [Chemical 8]

( _I 〖)

In the formula (Π), R ³ is an alkyl group having 1 to 20 carbon atoms, an aryleno group, an arylalkyl group, Y is a single bond, a polymethylene group having 1 to 10 carbon atoms, an alkylene group, and an alkylidene Ri, an integer from 0 to 4, pi from 0.00 to 1.00, a number from 1.00, qi to an integer from! To 500. When there are a plurality of R ³ forces S, a plurality of R ³ may be the same or different.

[0023] In the polycarbonate monohydrogenated polybutadiene copolymer of the present invention, the content of the hydrogenated polybutadiene portion is preferably set to 0.:! To 50 mass%. If the content of the hydrogenated polybutadiene portion is in the range of 0.:! To 50 mass%, compatibility can be exhibited. A more preferable content of the hydrogenated polybutadiene part is 0.5 to 40% by mass, and particularly preferably from! To 30% by mass.

The polycarbonate-hydrogenated polybutadiene copolymer of the present invention can have a viscosity average molecular weight of 10,000 to 50,000. US Occupancy Average Molecular Weight 10,000 to 50,0 If it is in the range of 00, when melt-kneaded as a compatibilizing agent, it contributes to homogenization of the polyolefin resin and polycarbonate resin, reduces the polyolefin domain, suppresses delamination of the molded product, and mechanical properties. Can be improved. More preferred viscosity average molecular weight f, 11,000 to 40,000, especially 13,000 to 30,000.

[0024] Method for producing polycarbonate monohydrogenated polybutadiene copolymer

The method for producing a polycarbonate-hydrogenated polybutadiene copolymer of the present invention comprises producing a polycarbonate oligomer by reacting an aromatic dihydroxy compound (A) represented by the following general formula (ΠΙ) with a carbonyl source. The polycarbonate oligomer, the aromatic dihydroxy compound (B) represented by the following general formula (IV), and the aromatic dihydroxy compound (A) are reacted in a mixed solution of an organic solvent and an alkaline aqueous solution. To do.

The polycarbonate-hydrogenated polybutadiene copolymer of the present invention can also be produced by a transesterification method or an oxidative carbonylation method other than the interfacial polycondensation method described above.

Below, the substance used for manufacture of the polycarbonate monohydrogenated polybutadiene copolymer and polycarbonate resin composition of this invention is demonstrated.

[0025] 1. Aromatic dihydroxy compound (A)

As the aromatic dihydroxy compound (A) used in the present invention, the general formula (III)

[0026] [Chemical 9]

(Where

R ² , X, m and n are the same as described above. )

[0027] An aromatic dihydroxy compound having about 12 to 37 carbon atoms is used.

[0028] Here, there are various aromatic dihydroxy compounds represented by the general formula (III), and 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. Masle. Bivalent phenols other than bisphenol A include 1,1_bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 9,9-bis (4-hydroxy) 9,9-bis (3-methyl 4-hydroxyphenol) fluorene; bis (4-hydroxyphenol) cycloalkane; bis (4-hydroxyphenol) sulfide; bis (4 Bis (4-hydroxyphenyl) other than bisphenol monourea such as bis (4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) ether; Compound or halogenated bisphenols such as 2,2_bis (3,5_dibromo_4-hydroxyphenol) propane; 2,2_bis (3,5-dicyclo _4-hydroxyphenyl) propane And the like. When these phenols have an alkyl group as a substituent, the alkyl group is preferably an alkenoquinole group having 8 to 8 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms. These aromatic dihydroxy compounds may be used alone or in combination of two or more.

[0029] 2. Phenolic-terminated hydrogenated polybutadiene (B)

Formula (IV)

[0030] [Chemical 10]

(Wherein R ³ , Y, p, q and r are the same as above.)

[0031] The phenol-terminated hydrogenated polybutadiene (B) represented by the general formula (V)

[0032] [Chemical 11]

(In the formula, Y, p, and q are the same as above.)

[0033] It is obtained by a transesterification reaction between a hydroxyl-terminated hydrogenated polybutadiene (C) represented by the formula (II) and a hydroxybenzoic acid ester derivative (D) represented by the general formula (VI). [0034] [Chemical 12]

(Wherein R ⁵ is a lower alkyl group, and R ³ and r are as defined above.)

Since the hydroxyl-terminated hydrogenated polybutadiene (C) represented by the formula (V) is obtained by hydrogenating polybutadiene, a small amount of double bonds are represented by the phenol-terminated hydrogenated polybutadiene (B) represented by the general formula (IV). ) Can be used as long as it does not affect the physical properties.

In addition, due to the polymerization of butadiene, the bonding force at 1,4 one or 1,2— can be used in the range of 0.00 ≤ ρ ≤ 1.00 where the ratio is unlimited.

Y is a single bond, a polymethylene group having 1 to 10 carbon atoms, an alkylene group or an alkylidene group, preferably an ethylene group or a propylene group [(HO)-[CH (CH) -CH]-(C)].

qi:!-500, preferably ί ::-200, more preferably ί-5: 150. As hydroxybenzoic acid and peroxyester derivative (D), R ⁵ is preferably a methyl group, an ethyl group, a η-propyl group, a η-butyl group, or the like.

A commercially available hydroxyl-terminated hydrogenated polybutadiene (C) is KRASOL HLBP_P300 (Y: ethylene group, p: 0.65, q: 66) manufactured by Sartoma. It is prepared by terminating polybutadiene with ethylene oxide followed by hydrogenation. In the examples of this application, KR

ASOL HLBP — P300 is used.

A phenol-terminated hydrogenated polybutadiene is obtained by an ester exchange reaction between a hydroxyl-terminated hydrogenated polybutadiene and a hydroxybenzoic acid ester derivative, but the terminal reaction rate may not necessarily be 100%. Those having a reaction rate of 50% or more can be used.

The present invention also provides a hydrogenated polybutadiene represented by the general formula (IV) and having a phenolic hydroxyl group at the terminal.

[0036] 3. Carbonyl source As the carbonyl source of the polycarbonate used in the present invention, phosgene used in interfacial polycondensation of general polycarbonates, triphosgene, bromophosgene and the like can be used. In the case of the transesterification method, carbon monoxide or the like can be used in the case of the diaryl carbonate isokinetic oxidative carbonyl method.

[0037] 4. End terminator

The polycarbonate end-stopper used in the present invention is not particularly limited to phenol, o _, m-, p _ cresol monole, ρ-tert-butinolephenol, ρ-tert-aminophenol, p _tert-octylphenol, p_cuminophenol, p-methoxyphenol, p_phenol, and the like. Of these, p_tert_butylphenol, p-tamylphenol, ρ-tert-octylphenol, and phenol are preferred.

[0038] 5. Polycarbonate monohydrogenated polybutadiene copolymer

The molecular weight and copolymerization ratio of the copolymer are not particularly specified, but the viscosity average molecular weight (Mv) is preferably 10,000 to 50,000 from the viewpoint of the viscosity used as a compatibilizing agent. 000-40,000 is preferred, 13,000-30,000 more preferred.

In addition, the hydrogenated polybutadiene content is preferably 0.:! To 50% by mass from the viewpoint of the balance between the development of the function as a compatibilizing agent and the physical properties of the resin composition, and 0.5 to 40% by mass is preferable. More preferable:! To 30% by mass is more preferable.

[0039] 6. Solvent, alkaline aqueous solution

In the interfacial polycondensation method, which is the production method of the present invention, various inert organic solvents such as dichloromethane (methylene chloride); chloroform; tetrasalt-carbon, 1, 1, -dichloroethane, 1, 2, —Dichloroethane; 1, 1, 1 trichloroethane; 1, 1,2-trichloroethane; 1, 1,1,2-tetrachloroethane; 1, 1, 1,2-tetrachloroethane; pentachloro Ethane; chlorinated hydrocarbons such as black benzene, toluene, and acetophenone. These organic solvents may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferred.

Examples of the alkali used in the preparation of the aqueous alkali solution include sodium hydroxide, potassium hydroxide, cesium hydroxide and the like. Among these, sodium hydroxide and potassium hydroxide are preferred, and sodium hydroxide is particularly preferred. is there. In the case of producing by a transesterification method, no solvent is required.

[0040] Furthermore, in the case of the oxidative carbonylation method, examples of the solvent include dichloromethane, chloroform, 1,2-dichloroethane, acetophenone, γ-butyrolataton, and tetrahydrofuran. A solvent having a carbonate bond is also useful. For example, dimethyl carbonate, jetino carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, diaryl carbonate, allyl methyl carbonate, bis (2-methoxyphenol) carbonate, vinylene carbonate, dibenzenol carbonate , Di (0-methoxyphenyl) carbonate, and methyl ethyl carbonate. Of these, propylene carbonate is preferred.

[0041] 7. Catalyst

In the interfacial condensation method, which is the production method of the present invention, a phase transfer catalyst such as a tertiary amine or a salt thereof, a quaternary ammonium salt, a quaternary phosphonium salt, or the like can be preferably used as the catalyst.

Examples of tertiary amines include triethylamine, tributylamine, Ν, Ν-dimethyl hexylamine, pyridine, dimethylaniline and the like, and examples of tertiary amine salts include those of tertiary amines. Examples include hydrochloride and bromate. Examples of the quaternary ammonium salt include trimethylbenzyl ammonium chloride, trioctylmethyl ammonium chloride, tetraptyl ammonium chloride, and tetraptyl ammonium bromide. Examples thereof include nium chloride and tetrabutylphosphonium bromide. These catalysts may be used alone or in combination of two or more. Of the above catalysts, tertiary amines are preferred, and triethylamine is particularly preferred.

[0042] Various transesterification catalysts can be used in the transesterification method, such as alkali metals (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metals, and the like. Examples thereof include nitrogen-containing basic compounds such as compounds, amines, and quaternary ammonium salts, or boron compounds.

Specific examples of the nitrogen-containing basic compound include trihexylamine, tetramethylammonium hydroxide, tetraptylammonium hydroxide, and dimethylpyridine. Used frequently. Examples of the boron compound include boric acid, trimethyl borate, triethyl borate, tryptyl borate, triheptyl borate, triphenyl borate, and trinaphthyl borate.

[0043] As the catalyst in the oxidative carbonyl drought method, catalysts in which various palladium compounds and redox agents are combined are used. Examples of the palladium compound include palladium chloride (11), carbonyl palladium chloride, palladium acetate (Π), dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) palladium (Π), and the like. These palladium compounds may be used alone or in combination of two or more.

Examples of redox agents include lanthanides, transition metals of Groups 5-7 of the periodic table, chromium, manganone, iron, cobalt, nickel, copper, and the like, with cobalt being preferred. Cobalt compounds such as cobalt chloride (Π) and cobalt acetate (Π) are suitable. Of these, salty cobalt (II) is preferred.

In the production of the polycarbonate monohydrogenated polybutadiene copolymer by the interfacial polycondensation method of the present invention, first, the aromatic dihydroxy compound (A) [hereinafter referred to as divalent phenol (A). ] And a carbonyl source such as phosgene are reacted to produce a polycarbonate oligomer.

In this reaction, a polycarbonate oligomer is obtained by preparing an alkaline aqueous solution containing the raw material divalent phenol (A) and reacting it with phosgene in the presence of an inert organic solvent.

[0045] In this case, the aqueous alkali solution preferably has a concentration of 1 to 15% by mass. Further, the content of the divalent phenol (A) in the alkaline aqueous solution is usually selected in the range of 0.5 to 20% by mass. Furthermore, the amount of the inert organic solvent used should be selected so that the volume ratio of the organic phase to the aqueous phase is 5 Zl to 7 Zl, preferably 2 Zl to 4 Zl. The reaction temperature is usually selected in the range of 0 to 50 ° C, preferably 5 to 40 ° C.

In this reaction, after reacting phosgene or the like, the reaction can be further carried out using an alkaline aqueous solution containing divalent phenol (A), a part of the terminal terminator and, if desired, a catalyst.

[0046] After the reaction, the aqueous phase and the polycarbonate oligomer are obtained by an operation such as standing or centrifugation. Into an organic phase containing. The organic phase can be used in the next step without isolating the polycarbonate oligomer.

Next, the polycarbonate oligomer obtained above, the above-mentioned phenol-terminated hydrogenated polybutadiene (B) and divalent phenol in the presence of the remaining end-termination agent, a catalyst used as required, an alkaline aqueous solution and an inert organic solvent. (A) is usually subjected to interfacial polycondensation at a temperature in the range of 0 to 50 ° C, preferably 5 to 40 ° C.

Examples of the alkali, the inert organic solvent and the catalyst used in this case are the same as those described in the production of the polycarbonate oligomer. The volume ratio of the organic phase to the aqueous phase in this interfacial polycondensation is the same as described above.

After the reaction, the reaction solution is appropriately diluted with an inert organic solvent and then separated into an aqueous phase and an organic phase containing a polycarbonate-hydrogenated polybutadiene copolymer by standing or centrifuging.

Finally, the polycarbonate monohydrogenated polybutadiene copolymer solution thus obtained is washed successively with an aqueous alkali solution, an acid aqueous solution and water, and then the polycarbonate monohydrogenated polybutadiene copolymer is isolated and recovered.

[0047] Next, the polycarbonate resin composition of the present invention will be described.

The polycarbonate resin composition of the present invention comprises the above polycarbonate-hydrogenated polybutadiene copolymer per 100 parts by mass in a mixture of 45 to 99% by mass of polycarbonate resin (1) and polyolefin resin (55 to 1% by mass). (iii) O .: It is obtained by blending! ~ 30 parts by mass and melt-kneading.

[0048] 8. Polycarbonate resin

The viscosity average molecular weight (Mv) of the polycarbonate resin (i) used in the polycarbonate resin composition of the present invention is preferably 10,000 to 50,000, more preferably 1,000 to 40,000, and more preferably 13,000 to 30,000. I like it. In the range of rice occupancy average molecular weight (Mv) from 0,000 to 50,000, the mechanical strength of the resin composition is satisfactory, and injection molding is possible.

[0049] 9. Polyolefin resin

The polyolefin resin (ii) used in the polycarbonate resin composition of the present invention is not particularly limited, for example, ethylene, propylene, butene-1, 4-methyl-pentene-1, etc. Is a homopolymer of ethylene and propylene, butene-1, pentene-1, hexene-1, heptene-1, otaten-1, 4-methyl-pentene-1, etc. Polymers, copolymers of propylene such as propylene and ethylene, butene-1, pentene-1, hexene-1, heptene-1, otaten-1, 4-methyl-pentene_1, butene-1 and ethylene And copolymers of olefins such as propylene, pentene-1, hexene-1, heptene-1, otaten-1, and 4-methyl-pentene_1. The copolymer may be a random copolymer or a block copolymer. In addition, the polyolefin resin (Π) may be one kind or a mixture of two or more kinds.

[0050] The melt index (MI) of the polyolefin resin (ii) is preferably a measurement method according to JIS K7210: 99, preferably f 0.1 to lOOg / 10 minutes, more preferably 0.00. 4 to 80 g / l0 min.

In the polycarbonate resin composition of the present invention, the mixing ratio of the polycarbonate resin (i) and the polyolefin resin (ii) is 45 to 99% by mass for the former and 55 to 1% by mass for the latter. A preferable mixing ratio is 50 to 98% by mass for the former and 50 to 2% by mass for the latter.

Further, the polycarbonate monohydrogenated polybutadiene copolymer (iii) is used in an amount of 0.:! To 30 per 100 parts by mass of the mixture of the polycarbonate resin (i), the polycarbonate resin (i) and the polyolefin resin (ii). It mix | blends in the ratio of a mass part.

If this blending amount is 0.1 parts by mass or more, it is effective for compatibilization of the polycarbonate resin and the polyolefin resin, and the polycarbonate resin composition has the ability to reduce the polyolefin domain. It can be suppressed, and mechanical properties such as low-temperature impact properties are improved. On the other hand, when the amount is 30 parts by mass or less, the polycarbonate resin composition can suppress other physical properties such as mechanical properties from being impaired.

[0051] Furthermore, in the present invention, mechanical properties such as impact resistance can be further improved by using a compatibilizing aid as the component (iv). In the present invention, the type of the compatibilizing aid used as the compatibilizing aid (iv) component is not particularly limited, but it is referred to as “styrene-ethylene / butylene-styrene block copolymer” (hereinafter referred to as “SEBS”). ) Is most preferred.

In addition, the following general formula (VII) or (VIII) χ- (γ-χ) ••• (νπ)

n

(x-Y) ■■■ (vm)

n

Is also preferably used as a compatibilizing aid. X in the general formulas (VII) and (VIII) is a styrene polymer block, and in the formula (VII), the degree of polymerization may be the same or different at both ends of the molecular chain. Y is at least one selected from the isoprene polymer block, hydrogenated butadiene polymer block, and hydrogenated isoprene polymer block. N is an integer of 1 or more.

[0052] The content of the X component in the block copolymer is 20 to 80% by mass, preferably 30 to 70% by mass. If this amount is less than 20% by mass, the rigidity of the resin composition tends to decrease, and if it exceeds 80% by mass, the molding strength and impact strength tend to decrease. The number average molecular weight per single block of the X component should be in the range of 5,000 to 200,000, and the number average molecular weight per block of the Y component should be in the range of 5,000 to 200,000. I want it. When the number average molecular weight per single block of the X component is less than 5,000 or when the number average molecular weight per block of the Y component is less than 5,000, the mechanical properties of the resin composition tend to be insufficient. If the number average molecular weight per single block of the X component exceeds 200,000 or the number average molecular weight per block of the Y component exceeds 200,000, the molding processability of the resin composition tends to decrease, which is not preferable. . Further, the number average molecular weight of the entire block copolymer should be in the range of 10,000 to 400,000. S The mechanical properties are inferior when the number average molecular weight is less than 10,000, and molding processing is in excess of 400,000. This is not preferable because of a tendency to deteriorate. By adding a compatibilizing aid, impact resistance can be further improved.

[0053] Specific examples of such block copolymers include styrene monohydrogenated butadiene monostyrene triblock polymer, styrene monoisoprene monostyrene triblock polymer, styrene-hydrogenated isoprene monostyrene triblock polymer, styrene monohydric acid. Examples thereof include an isoprene block polymer, a styrene monoisoprene block polymer, and a styrene monohydrogenated butadiene dib polymer. Other compatibilizers include acid-modified EPR, epoxy-modified EPR, acid-modified polyolefin, epoxy-modified polyolefin, amino-modified EPR, amino-modified polyolefin, acid-modified EPR, or acid-modified polyolefin / epoxy resin. Etc. The blending amount of the ( _lv ) component is determined according to the polyolefin resin (i) and the polyolefin resin (ii

), That is, 0.5 to 10 parts by weight, preferably:! To 8 parts by weight, particularly preferably 2 to 6 parts by weight with respect to 100 parts by weight of the component ((i) + (ii)). . If it is 10 parts by mass or more, the rigidity will be insufficient. Less than 0.5 parts by mass, no improvement in impact resistance is observed. In the present invention, the compatibilizing aid may be used alone or in combination of two or more.

[0054] 10.Other

Moreover, you may mix | blend various additives with the polycarbonate resin composition of this invention in the grade which does not impair performance. Examples of additives include hindered phenolic and ester antioxidants, hindered amine light stabilizers, flame retardants, flame retardants, colorants, antistatic agents, and anti-blocking agents. Agents, weathering agents, mold release agents, and lubricants.

In addition to the above additives, fiber fillers such as glass fiber, carbon fiber and aramid fiber, metal fibers such as copper or brass, whiskers such as potassium titanate, magnesium oxysulfate, aluminum borate, Powdery inorganic fillers such as talc, calcium carbonate, magnesium carbonate, silicic force, carbon black, titanium oxide, clay, my strength, magnesium hydroxide, and aluminum hydroxide may be added as appropriate.

[0055] The polycarbonate resin composition of the present invention can be obtained by blending the above-described components and, if necessary, melt-kneading. For blending and melt-kneading, conventional methods can be adopted, such as ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single screw extruder, twin screw extruder, conida, and multi-screw single extruder. Etc. The heating temperature for melt kneading is usually 210 to 260 ° C.

The present invention also provides a molded article obtained by melt-molding the polycarbonate resin composition of the present invention.

[0056] According to the present invention, a polycarbonate monohydrogenated polybutadiene copolymer having a specific structure is effective for compatibilization of a polycarbonate resin and a polyolefin resin, and the polycarbonate monohydrogenated polybutadiene copolymer is blended. Since the polycarbonate resin composition of the present invention can reduce the polyolefin domain, Excellent mechanical properties such as low-temperature impact resistance that do not exhibit separation.

Example

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0058] Production Example 1 (Production of polycarbonate oligomer)

To 5 mass ^_0/0 aqueous sodium hydroxide 400 L, construed dissolved the Bisufuenonore A (BPA) of 60 kg, was prepared aqueous sodium hydroxide bisphenol A. Next, an orifice plate was passed through a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m at a flow rate of 138 L / hour of bisphenol A sodium hydroxide aqueous solution kept at room temperature and a flow rate of methyl chloride of 69 L / hour. Then, phosgene was co-flowed and blown at a flow rate of 10.7 kg / hour, and the reaction was continued for 3 hours. The tubular reactor used here is a double tube, and cooling water was passed through the jacket to maintain the reaction liquid discharge temperature at 25 ° C. The pH of the effluent was adjusted to be 10-11. The reaction solution thus obtained was allowed to stand to separate and remove the aqueous phase, and a methylene chloride phase (220 L) was collected, and 170 L of methylene chloride was further added thereto, and the resulting mixture was thoroughly stirred. An oligomer (concentration 317 g / L) was used. The degree of polymerization of the PC oligomer obtained here was 3 to 4, and the concentration of the black mouth formate group was 0.73 molZL.

[0059] Production Example 2 (Production of phenol-terminated hydrogenated polybutadiene)

Put 500g of KRAS OL HLBP-P300, 40g of methyl p-hydroxybenzoate and 0.25g of dibutyltin oxide as hydroxyl group-terminated hydrogenated polybutadiene by autoclaving at 220 ° C under nitrogen atmosphere and atmospheric pressure. C, heated and stirred for 6 hours, and the methanol was distilled off. Thereafter, the pressure was reduced to remove unreacted methyl p-hydroxybenzoate. Upon cooling, the desired phenol-terminated hydrogenated polybutadiene was obtained. It is a viscous liquid at room temperature. The terminal fraction was calculated by iH-NMR measurement, and the calculated terminal reaction rate was 95%.

Example 1 (Production of polycarbonate monohydrogenated polybutadiene copolymer A)

Diluted by adding 6 L of methylene chloride to 10 L of the polycarbonate oligomer obtained in Production Example 1, and 178 g of phenol-terminated hydrogenated polybutadiene obtained in Production Example 2 and p-tert-butylphenol 68 g of glue was added and dissolved. Thereto was added an aqueous sodium hydroxide solution (NaH: 60 g, 350 ml) and 6.3 ml of triethylamine, and the mixture was stirred at 300 i "pm for 1 hour. Then, an alkaline aqueous solution of bisphenol A (bisphenol A: 712 g, hydroxylated) Sodium: 416 g, water: 5 L) was added, and the mixture was stirred for 1 hour at 500 rpm After stirring for 1 hour, 10 L of methylene chloride and water: 10 L were added and stirred for 15 minutes, and then the methylene chloride phase was separated by standing. The methylene chloride phase was washed with 0.03 mol ZL aqueous sodium hydroxide solution, 0.2 mol / L hydrochloric acid and water (twice) in this order, and then the methylene chloride phase was concentrated and acetone was added for crystallization. The solvent was removed to obtain a flaky polymer, which was dried with hot air at 120 ° C. for 12 hours, and the obtained polycarbonate-hydrogenated polybutadiene copolymer A had a viscosity average molecular weight (Mv) of 22,000. -ΝΜ Hydrogenated poly Diene content 4. was 5 wt%.

The viscosity average molecular weight (Mv) was calculated from the following equation by measuring the intrinsic viscosity at 20 ° C in methylene chloride using an Ubbelohde viscometer.

[77] = 1 · 23 X 10— ⁵ · Μν ⁰ · ⁸³

Example 2 (Production of polycarbonate monohydrogenated polybutadiene copolymer cocoon)

A polycarbonate monohydrogenated polybutadiene copolymer B was obtained in the same manner as in Example 1, except that 178 g of phenol-terminated hydrogenated polybutadiene was changed to 356 g. The viscosity average molecular weight (Mv) was 22,400, and the hydrogenated polybutadiene content was 8.9% by mass by NMR measurement.

[0062] Examples 3 to 9, Comparative Examples 1 to 2

Under the composition and temperature conditions shown in Table 1, using a twin-screw kneader (TEM-35B, manufactured by Toshiba Machine Co., Ltd.), pellets were produced by melt-kneading extrusion at a screw speed of 300 rpm and 260 ° C. The raw material composition is polycarbonate resin (i), polycarbonate: Teflon FN1700 (Mv: 17,400) manufactured by Idemitsu Kosan Co., Ltd., polyolefin resin (ii), block polypropylene: Prime Polypro J_785H (MI: 1 lg / 10 min), and high-density polyethylene: Asahi Kasei Corporation Suntech J_300 (MI: 41 gZlO min), Compatibilizer (iv) SEBS, Asahi Kasei Corporation

Using the copolymer A and copolymer B obtained in Example 1 and Example 2 as Tuftec H-1050, a polycarbonate monohydrogenated polybutadiene copolymer (iii), listed in Table 1. It mix | blended with the mass% of the mounting. The mixing ratio of the polycarbonate resin (i) and the polyolefin resin (ii) was as follows: Examples 3, 5, 7, 8 and 9 were 79% by mass for the polycarbonate resin (1) and 21% by mass for the polyolefin resin (ii). Examples 4 and 6 are polycarbonate resin (1) 78% by mass and polyolefin resin (ii) is 22% by mass. In Table 1, copolymer (m) and compatibilizer (iv) are also shown. It was expressed in mass% of the total including.

[0063] Evaluation

The pellets of the obtained Examples and Comparative Examples were formed on a 100-ton injection molding machine (model name: IS-100EN, manufactured by Toshiba Machine Co., Ltd.) under conditions of a molding temperature of 270 ° C and a mold temperature of 80 ° C. A test piece (test piece) was prepared and subjected to the following measurements.

(1) Melt flowability MFR (melt flow rate): 280 according to JIS K 7210. C, Under a pressure of 15.7 MPa, the amount of molten resin (mlZsec) flowing out from a nozzle having a diameter of 1 mm and a length of 10 mm was measured.

(2) Tensile strength at break: Measured according to JIS K 7133.

(3) IZOD (Izod impact strength), (wall thickness: 3.2 mm) Measured at 0 ° C according to ASTM D256.

(4) Chemical resistance: Conforms to the evaluation method (limit strain due to 1/4 ellipse). A sample piece (thickness = 3 mm) was fixed on the 1/4 ellipse surface shown in Fig. 1 (perspective view), and a mixed solution of toluene / isooctane = 4/6 was applied to the sample piece and held for 48 hours. The minimum length (X) at which cracks occurred was read, and the critical strain (%) was determined from the following equation (1).

[0064] [Equation 1] b 1 b

Limit strain (%) -—— [1— (——-) X ² ] ³ , ² ■ txl 0 0

Z a ² a ² a

(1)

(t: thickness of specimen) These results are summarized in Table 1.

[0065] [Table 1]

[0066] As is apparent from the results of the examples in Table 1, each of the examples using the polycarbonate resin composition of the present invention is a resin composition in which a polycarbonate resin and a polyolefin resin are simply melt-kneaded. Compared to Examples 1 and 2, the tensile strength and IZOD impact strength were improved, and no delamination occurred even when the specimen was broken after the tensile test.

In addition, it can be understood that the IZ OD impact strength at a low temperature of 0 ° C. is improved and the fluidity is improved as compared with Comparative Example 3 consisting only of polycarbonate resin.

Furthermore, the chemical resistance of the mixed solution of toluene Z isooctane = 4Z6 is also excellent. From these results, it is considered that the polycarbonate-hydrogenated polybutadiene copolymer acts as a compatibilizing agent, reduces the polyolefin domain, suppresses delamination, and improves mechanical properties and chemical resistance. It is done.

Industrial applicability

[0067] The polycarbonate resin composition of the present invention uses a polycarbonate hydrogenated polybutadiene copolymer having a specific structure and is compatible with the polycarbonate resin and the polyolefin resin, so that the polyolefin domain can be reduced. It is a polycarbonate resin composition excellent in low temperature impact resistance, fluidity, and chemical resistance that does not exhibit delamination after molding, and can be suitably used for various molded products that require these performances. Further, the polycarbonate-hydrogenated polybutadiene copolymer of the present invention can be effectively used as a compatibilizing agent in the production of a polycarbonate resin composition, and the hydrogenated polybutadiene of the present invention is used for the polycarbonate-hydrogenated polybutadiene copolymer. It can be suitably used for polymer production.

Furthermore, the method for producing a polycarbonate-hydrogenated polybutadiene copolymer of the present invention is a method that can be efficiently produced with high reproducibility, and can be used for producing the polycarbonate monohydrogenated polybutadiene copolymer.

Claims

A polycarbonate-hydrogenated polybutadiene copolymer having a repeating unit (I) represented by the following general formula (I) and a repeating unit (Π) represented by the following general formula (Π).

[Chemical 1]

[In the formula, R ¹ and are each a halogen atom (eg, chlorine, bromine, fluorine, iodine), an alkoxy group, an ester group, a carboxyl group, a hydroxyl group, an alkyl group having from 8 to 8 carbon atoms, or the total number of carbon atoms. It has an alkyl group on the ring of 6 to 20 and may be an aromatic group, and may be bonded to either the o_ position or the m_ position. If the R ¹ and R ² are a plurality of each, even each R ¹ and R ² are identical to each other or may be different. X is a single bond, a polymethylene group having 1 to 20 carbon atoms, an alkylene group, an alkylidene group, a cycloalkylene group, one S-, one SO-, -SO-, one hundred one, one one C01 bond or general formula

[Chemical 2]

And a fluorene residue, m and n represent an integer of 0-4. ]

[Chemical 3]

[In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryleno group, and an arylalkyl group, Y represents a single bond, a polymethylene group having 1 to 10 carbon atoms, an alkylene group, an alkylidene group, rf or It is an integer from 0 to 4, pf or from 0.00 to 1.00, qi or from! To 500. R ³ months If you have more than one, even multiple of R ³ are identical to each other, it may also have a different record,. ]

[2] The poly force-bonate monohydrogenated polybutadiene copolymer according to claim 1, wherein the content force of the hydrogenated polybutadiene portion is 0.:! To 50% by mass.

[3] The polycarbonate one-to-hydrogenated polybutadiene copolymer according to claim 1 or 2, having a viscosity average molecular weight of 10,000 to 50,000.

[4] A polycarbonate oligomer is produced by reacting the aromatic dihydroxy compound (A) represented by the following general formula (ΠΙ) with a carbonyl source, and the polycarbonate oligomer and the following general formula (IV) The aromatic dihydroxy compound (B) represented and the aromatic dihydroxy compound (A) are reacted in a mixed solution of an organic solvent and an aqueous alkali solution, according to any one of claims 1 to 3. Process for producing a polycarbonate monohydrogenated polybutadiene copolymer.

[Chemical 4]

[In the formula, R ¹ and R ² are each a halogen atom (for example, chlorine, bromine, fluorine, iodine), an alkoxy group, an ester group, a carboxyl group, a hydroxyl group, an alkyl group having from 8 to 8 carbon atoms, or all The ring has an alkyl group on the ring having 6 to 20 carbon atoms, and may be an aromatic group, and may be bonded to either the o-position or the m-position. If the R ¹ and R ² are a plurality of each, even each R ¹ and R ² are identical to each other or may be different. And X is a single bond , C1-C20 polymethylene group, group, cycloalkylene group, cycloalkylidene group, SSO 0, CO-bond or general formula

[Chemical 5]

And a fluorene residue, m and n represent an integer of 0-4. ]

[Chemical 6]

[In the formula, R ³ is an alkyl group having 1 to 20 carbon atoms, an arylene group, an aryl alkyl group, Y is a single bond, a polymethylene group having 1 to 10 carbon atoms, an alkylene group, an alkylidene group, and r is 0 to 4 An integer, p. 00 ~: The number of 1.00, q is an integer of:! ~ 500. When there are a plurality of R ^{3 s} , they may be the same as or different from each other. ]

A mixture of polycarbonate resin (i) 45 to 99 weight ^_0/0 and polyolefin resin (55-1 wt%, the weight per 100 parts by weight, polycarbonate monohydrogen polybutadiene copolymerization according to claim 1 Combined (iii) O .: A polycarbonate resin composition comprising! -30 parts by mass, melt-kneaded.

The polycarbonate monohydrogenated polybutadiene copolymer according to any one of claims 1 to 3 per 100 parts by mass of a mixture of polycarbonate resin (i) 45 to 99% by mass and polyolefin resin (55 to 1% by mass) iii) O .:! ~ 30 parts by weight and styrene ethylene Compatibilizing aid made of styrene block copolymer (iv) 0.5-: 10 parts by mass

A polycarbonate resin composition obtained by melt-kneading.

[7] A molded article obtained by melt-molding the polycarbonate resin composition according to claim 5 or 6.

[8] A hydrogenated polybutadiene having a phenolic hydroxyl group at the terminal represented by the general formula (IV).